(12) United States Patent (10) Patent No.: US 9,708,528 B2 Yam Et Al

USOO9708528B2

(12) United States Patent (10) Patent No.: US 9,708,528 B2 Yam et al. (45) Date of Patent: Jul.18, 2017

(54) ROBUST PHOTOCHROMIC COMPOUNDS USPC ...... 556/400 WITH SILICON- OR See application file for complete search history. PHOSPHORUS-CONTAINING HETEROCYCLIC RING AND THE (56) References Cited PRODUCTION THEREOF U.S. PATENT DOCUMENTS (71) Applicant: THE UNIVERSITY OF HONG 5,175,079 A 12/1992 Van et al. KONG, Hong Kong (HK) 5,183.726 A 2/1993 Taniguchi et al. 5,443,940 A 8, 1995 TatezOno et al. (72) Inventors: Vivian Wing-Wah Yam, Hong Kong 5,622,812 A 4/1997 TatezOno et al. (HK); Jacky Chi-Hung Chan, Hong 6,359,150 B1 3/2002 Fukudome et al. Kongs (HK). Iok-Lai Wong Hongs 2003,6.479,604 OO86978 A1B1 1 5.20031/2002 Kim et al. Kong (HK); Nathan Man-Wai Wu, 2003. O130456 A1 7, 2003 Kim et al. Hong Kong (HK) 2007/0O82977 A1 4/2007 Shibahashi et al. (73) Assignee: THE UNIVERSITY OF HONG FOREIGN PATENT DOCUMENTS KONG, Hong Kong (HK) WO 2007-105699 9, 2007 (*) Notice: Subject to any disclaimer, the term of this WO 2013-044371 4/2013 patent is extended or adjusted under 35 U.S.C. 154(b) by 26 days. OTHER PUBLICATIONS (21) Appl. No.: 14/734,233 CAS Registry of the Amer. Chem. Soc., Registry No. 1271102-02-3 y x- - - 9 (Mar. 28, 2011).* (22) Filed:1-1. Jun. 9, 2015 Tamao11974-11975* et al., Journal of the Amer. Chem. Soc. (1996), 118(47), O O Cipolloni et al., Journal of Physical Chem. (2008), 112, 4765 (65) Prior Publication Data 4771: US 2015/0361332 A1 Dec. 17, 2015 Yamaguchi et al., Tetrahedron Letters (2011), 52(43), 5601-5604.* Related U.S. Application Data k cited. by examiner (60) Provisional application No. 62/011,797, filed on Jun. Primary Examiner — Porfirio Nazario Gonzalez 13, 2014. Assistant Examiner — Kofi Adzamli (74) Attorney, Agent, or Firm — Amin, Turocy & Watson, (51) Int. Cl. LLP C07F 7/02 (2006.01) C09K 9/02 (2006.01) (57) ABSTRACT C07F 7/08 (2006.01) In one embodiment, provided are a new class of diaryle C7F 9/6568 (2006.01) thene-containing photochromic compounds with the incor (52) U.S. Cl. poration of silicon- or phosphorus-containing heterocycles CPC ...... C09K 9/02 (2013.01); C07F 7/0814 into the “ethene' part of the diarylethene backbone that has (2013.01); C07F 7/0827 (2013.01); C07F been shown to be capable of displaying tunable, robust and 9/65685 (2013.01); C07F 9/65686 (2013.01); thermally stable photochromic properties. Also provided are C07F 9/65688 (2013.01); C09K2211/1029 methods for synthesizing these compounds, as well as uses (2013.01); C09K2211/1033 (2013.01); C09K of these compounds as these compounds may be used as the 221 1/1037 (2013.01); C09K 2211/1092 photochromic layer in an optical recording material and (2013.01); C09K 221 1/1096 (2013.01) other optical functioning devices. (58) Field of Classification Search CPC ...... C09K 9/02; C07F 9/6569; C07F 7/08 17 Claims, 6 Drawing Sheets U.S. Patent Jul.18, 2017 Sheet 1 of 6 US 9,708,528 B2

3OO 400 500 Wavelength 1 nm

Figure 1

open form close form

Figure 2 U.S. Patent Jul.18, 2017 Sheet 2 of 6 US 9,708,528 B2

3 o 9 O f C C

300 400 500 600 700 Wavelength 1 nm

Figure 3

9 o s O w O d C

300 400 500 600 Wavelength 1 nm

Figure 4 U.S. Patent Jul.18, 2017 Sheet 3 of 6 US 9,708,528 B2

3 s O f O c

300 400 500 600 700 800 Wavelength 1 nm

Figure 5

1.O

0.8 92 5 0.6

0.4 w 2. (r. 0.2

400 450 500 550 Wavelength 1 nm

Figure 6 U.S. Patent Jul.18, 2017 Sheet 4 of 6 US 9,708,528 B2

O 500 OOO 1500 2000 Times 1 minutes

Figure 7

O 500 OOO 1500 2000 Time 1 min

Figure 8 U.S. Patent Jul.18, 2017 Sheet 5 of 6 US 9,708,528 B2

0.00280 0.00285 0.00290 0.00295 0.00300

2000 4000 6000 8000 Time / S

Figure 10 U.S. Patent Jul.18, 2017 Sheet 6 of 6 US 9,708,528 B2

0.30

O.25 E o o 0.20 5 O.5

O O. 10 o s 0.05 o

O 5000 OOOO 15000 Time IS

Figure 11 US 9,708,528 B2 1. 2 ROBUST PHOTOCHROMC COMPOUNDS Amongst the many heterocycles, phospholes and siloles WITH SLICON- OR have been less extensively studied, but have recently PHOSPHORUS-CONTAINING attracted increasing interests due to their unusual electronic HETEROCYCLIC RING AND THE and optical properties and possible application as organic PRODUCTION THEREOF light-emitting devices (OLEDs). Recently, Yam and co workers Yam, V. W.-W.: Ko, C.-C.; Zhu, N.J. Am. Chem. CROSS REFERENCE TO RELATED Soc. 126, 12734 (2004): Yam, V. W.-W.; Lee, J. K.-W.: Ko, APPLICATION C.-C. Zhu, N.J. Am. Chem. Soc. 131, 912 (2009); Wong, H.-L.: Ko, C.-C.; Lam, W. H.; Zhu, N.; Yam, V. W.-W. This application claims priority to provisional application 10 Chem. Eur: J. 15, 10005 (2009); Poon, C.-T.: Lam, W. H.; Ser. No. 62/011,797, filed on Jun. 13, 2014, which is Yarn, V. W.-W. J. Am. Chem. Soc. 133, 19622 (2011) and incorporated herein by reference. other research groups Nakashima, T., Fujii, R.; Kawai, T. Chem. Eur: J. 17, 10951 (2011); Kühni, J.; Belser, P. Org. TECHNICAL FIELD Lett. 9, 1915 (2007) have shown that the incorporation of 15 heterocycles into the “ethene' part of the diarylethene Described herein relates to the design of novel photochro backbone, instead of derivatizing the pendants of the bis mic heterocyclic compounds and their photochromic stud (thienyl)perfluorocyclopentene core, can enrich the pho ies. The design of these photochromic compounds is based tochromic and photophysical behaviors. In spite of the on the cis-diarylethene structure, which forms part of the increasing interest in the use of phospholes and siloles and mono- or poly-heterocyclic compounds that contain a sili their derivatives for the fabrication of OLEDs, there are no con- or a phosphorus-containing heterocyclic ring. These examples on the use of functionalized phosphole and silole compounds can be used as the photochromic layer in an as the “ethene' part of the photochromic diarylethene back optical recording material and other optical functioning bone. devices. Further information can be found in U.S. Pat. Nos. 25 BACKGROUND 5,175,079, 5,183,726, 5,443,940, 5,622,812, and 6,359,150; Japanese patents JP 2-250877, JP 3-014538, JP 3-261762, JP Photochromism is defined as “a reversible transformation 3-261781, JP 3-271286, JP 4-282378, JP 5-059025, JP of a single chemical species being induced in one or both 5-222035, JP 5-222036, JP 5-222037, JP6-199846, JP directions by absorption of electromagnetic radiation, with 30 10-045732, JP 2000-072768, JP 2000-344693, JP 2001 two states having different distinguishable absorption spec 048875, JP 2002-226477, JP 2002-265468 and JP 2002 tra'. Photochromic compounds are compounds that possess 293784; and in Irie, M.; Mohri, M. J. Org. Chem. 53.803 at least two isomeric forms, which have different physical (1988): Nakamura, S.; Irie, M. J. Org. Chem. 53. 6136 properties. Such as absorption and emission properties, (1988); and Irie, M. Chem. Rev. 100. 1685 (2000). refractivity, and the like, and can be transformed from one 35 form to another by photo-excitations at prescribed wave SUMMARY lengths. The invention includes the use of mono- or poly-hetero Photochromism has been extensively studied due to its cyclic compounds to perturb the properties of the diaryle potential use for optical recording and other optical func thenes in the photochromic compounds. Described below is tioning devices. To be practically used as optical recording 40 a report of the design, synthesis and studies of cis-diaryle materials, both isomeric forms must be thermally stable and thene-containing compounds, with the incorporation of sili possess excellent durability for reversible photochromic con- or phosphorus-containing heterocycles into the reactivity. Diarylethene is one class of photochromic com “ethene' part of the diarylethene backbone. The photophysi pounds, which possesses all these necessary properties, and cal properties show the advantageous use as tunable, robust therefore is a suitable class of compounds for the construc 45 and thermally stable photochromic materials. tion of optical functioning devices. The cis-configuration of One consequence is to provide a new class of diaryle both aryl groups in the diarylethenes studied is generally thene-containing photochromic compounds with the incor fixed by an upper cycloalkane structure. Such as fluorinated poration of silicon- or phosphorus-containing heterocycles alicyclic group, aromatic group, anhydride and maleimide into the “ethene' part of the diarylethene backbone that has group. Apart from the difference in absorption characteris 50 been shown to be capable of displaying tunable, robust and tics and the like between the two forms and their thermal thermally stable photochromic properties. stabilities, the availability of desirable excitation wave lengths that can be tuned and selected for the photochromic Described herein are a new class of silicon- or phospho reactions also represents an important aspect in the design of rus-containing heterocyclic compounds of the formula: materials for optical functioning devices. 55 Even though there has been increasing interest in diary lethene-containing photochromic materials, most efforts (I) have been focused on the derivatization of the diarylper fluorocyclopentenes to tune the photophysical and pho tochromic behaviors while less efforts have been made in the 60 design and synthesis of different types of diarylethenes with excellent photochromic properties. However, the derivatiza tion of diarylperfluorocyclopentenes has been rather limited wherein X refers to heteroatoms including one or more of with most of the works mainly focused on modifications at silicon or phosphorus, A and B are cyclic structure deriva the Substituted aryl groups only. 65 tives, m and n are the number of rings in the cyclic structure The most commonly studied heterocycles include pyr derivatives and m and n are independently greater than or roles, thiophenes, indoles, thiazoles, imidazoles and others. equal to Zero; C and Dare heterocyclic groups, provided that US 9,708,528 B2 3 4 C and D are cyclizable by irradiation with light to form and D are cyclizable by irradiation with light to form cyclohexadiene ring for tuning the optical properties. cyclohexadiene ring for tuning the optical properties. Also described herein is an optical recording material Heterocyclic ring with X refers to the silicon- or phos containing a recording layer comprising of a photochromic phorus-containing heterocycles, wherein X includes, but not Substance that is capable of reversibly undergoing a color 5 limited to, SiRR', P(O)R, P(BH)R, P(BL)R, P(S)R, P(Se) change in such a manner that when photoirradiated with UV R, P(CH) R, P(SR)R, PR, P(R)R, P(WL)R, P(CrL)R, light, the photochromic Substance undergoes a color change P(MnL)R, P(MoL)R, P(ReL)R, P(PtL)R, P(PdL)R, and when irradiated with visible light or near-infrared radia P(CuI)R, P(CuIL)R, P(RuLs)R, P(IrLs)R, P(FeL)R, tion, the photochromic Substance returns to the initial color, P(RhL)R, P(RhL)R, P(CoL)R, P(NiL)R, P(AgI)R, 10 P(AgL)R, P(AuL)R, or P(AuL)R’ where R, R or L is in which information is recorded by irradiating the recording independently alkyl, alkenyl, alkynyl, alkylaryl, cycloalkyl, layer with light, wherein the photochromic Substance is a haloformyl, hydroxyl, aldehyde, carboxamide, amine, diarylethene-containing heterocycle derivatives of the for amino, alkoxy, azo, benzyl, carbonate ester, carboxylate, mula (I) as defined above. carboxyl, ketamine, isocyanate, isocyanide, isothiocyanate, 15 nitrile, nitro, nitroso, phosphine, phosphate, phosphono, BRIEF DESCRIPTION OF THE DRAWINGS phosphate, pyridyl, Sulfonyl, Sulfo, Sulfinyl, Sulfhydryl, halo, aryl, substituted aryl, heteroaryl, substituted heteroaryl or a FIG. 1 shows the UV-vis absorption spectral changes of 1 heterocyclic group, wherein X refers to P(CH)R or P(R')R. in degassed benzene upon excitation at 362 mm. and wherein P(CH)R or P(R')R can be having a counter FIG. 2 shows the photochromic reaction of compound 12. anion: OTf, PF, B.Ph., CIO, or halide ions, where R FIG. 3 shows the UV-vis absorption spectral changes of and R' are independently alkyl, alkenyl, alkylaryl, cycloal 12 in degassed benzene upon excitation at 391 nm. cyl, haloformyl, hydroxyl, aldehyde, carboxamide, amine, FIG. 4 shows the UV-vis absorption spectral changes of amino, alkoxy, azo, benzyl, carbonate ester, carboxylate, 23 in degassed benzene upon excitation at 360 nm. carboxyl, ketoamine, isocyanate, isocyanide, isothiocyanate, FIG. 5 shows the UV-vis absorption spectral changes of 25 nitrile, nitro, nitroso, phosphine, phosphate, phosphono, 33 in degassed benzene upon excitation at 360 nm. phosphate, pyridyl, Sulfonyl, Sulfo, Sulfinyl, Sulfhydryl, halo, FIG. 6 shows the emission spectral changes of 12 in aryl, substituted aryl, heteroaryl, substituted heteroaryl or a degassed benzene upon excitation at 391 nm. heterocyclic group. FIG. 7 shows a plot of ln(A/A) versus time for the In any R group or hydrocarbyl group (Such as alkyl, absorbance decay of 12 at 638 nm at various temperatures in 30 alkenyl, alkylaryl, cycloalkyl, haloformyl, hydroxyl, alde argon-flushed toluene solution; A denotes absorbance at time hyde, carboxamide, amine, amino, alkoxy, azo, benzyl, t and A. denotes the initial absorbance; solid lines represent carbonate ester, carboxylate, carboxyl, ketamine, isocya the theoretical linear fits. nate, isocyanide, isothiocyanate, nitrile, nitro, nitroso, phos FIG. 8 shows a plot of ln(A/A) versus time for the phine, phosphate, phosphono, phosphate, pyridyl, Sulfonyl, absorbance decay of 25 at 500 nm at 358 K in argon-flushed 35 sulfo, sulfinyl, sulfhydryl, halo, aryl, substituted aryl, het decahydronaphthalene solution; A denotes absorbance at eroaryl, Substituted heteroaryl or a heterocyclic group, for time t and A denotes the initial absorbance. example). Such group can contain 1 to 50 carbon atoms. In FIG. 9 shows the Arrhenius plot for the thermal backward another embodiment, any R group or hydrocarbyl group reaction of the closed form of 12 in argon-flushed toluene contains 1 to 25 carbon atoms. Solution. FIG. 10 shows the UV-vis absorbance changes of 6 at 444 40 Rings A and B are cyclic structure derivatives where the nm on alternate excitation at 380 and 444 nm over five cyclic structures are independently selected from a 5- or cycles in degassed benzene solution at 298 K. 6-membered arene, heteroacene or heterocycle known in the FIG. 11 shows the UV-vis absorbance changes of 23 at art. The arene, heteroacene or heterocycle can be benzene, 500 nm on alternate excitation at 360 and 500 nm over seven pyridine, thiophene, furan, pyrazole, imidazole, oxazole, 45 isoxazole, thiazole, isothiazole, isoquioline, pyrrole, pyra cycles in degassed benzene solution at 298 K. Zine, pyridazine, pyrimidine, benzimidazole, benzofuran, benzothiazole, indole, naphthalene, anthracene, pyrene, tri DETAILED DESCRIPTION azole, tetrazole, pyran, thiapyran, oxadiazole, triazine, tet Embodiments are directed to a new class of diarylethene razine, carbazole, dibenzothiophene, dibenzofuran, fluorene containing photochromic compounds with the incorporation 50 and derivatives thereof. Rings A and B can be unsubstituted or can be substituted of silicon- or phosphorus-containing heterocycles into the with one or more alkyl, alkenyl, alkynyl, alkylaryl, “ethene' part of the diarylethene backbone. The compounds cycloalkyl, haloformyl, hydroxyl, aldehyde, carboxamide, have the chemical structure shown in generic formula (I): amine, amino, alkoxy, azo, benzyl, carbonate ester, carboxy 55 late, carboxyl, ketamine, isocyanate, isocyanide, isothiocya nate, nitrile, nitro, nitroso, phosphine, phosphate, (I) phosphono, phosphate, pyridyl, Sulfonyl, Sulfo, Sulfinyl, sulfhydryl, halo, aryl, substituted aryl, heteroaryl, substi tuted heteroaryl or a heterocyclic group, and additionally, or 60 alternatively, any two adjacent Substituted positions of rings A and B together form, independently, a fused 5- or 6-mem bered cyclic group, wherein the said cyclic group is wherein X refers to heteroatoms including one or more of cycloalkyl, cycloheteroalkyl, aryl, or heteroaryl, and silicon or phosphorus, A and B are cyclic structure deriva wherein the fused 5- to 6-membered cyclic group may be tives, m and n are the number of rings in the cyclic structure 65 substituted with one or more of alkyl, alkenyl, alkynyl, derivatives and they are independently greater than or equal alkylaryl, cycloalkyl, haloformyl, hydroxyl, aldehyde, car to zero; C and D are heterocyclic groups, provided that C boxamide, amine, amino, alkoxy, azo, benzyl, carbonate US 9,708,528 B2 5 6 ester, carboxylate, carboxyl, ketoamine, isocyanate, isocya- -continued nide, isothiocyanate, nitrile, nitro, nitroso, phosphine, phos- R" phate, phosphono, phosphate, pyridyl, Sulfonyl, Sulfo, Sulfi- R" Y C nyl, sulfhydryl, halo, aryl, substituted aryl, heteroaryl, Substituted heteroaryl or a heterocyclic group. 5 W \ / \ R" Specific examples of the diarylethene-containing pho R" Y P D tochromic compounds of formula (I) include the following. R./\ E. R" R/ \

f 10 e- C R Y C R" C

W \ OSN P D it\ / P \ D / \ R / \ R" Si D 15 R. E. R. E.

R./ \,R. R" C R" C e- R" Y

N R" P D N R/\, E

In the above formulae (I), the R, R and R" may be alkyl, alkenyl, alkynyl, alkylaryl, cycloalkyl, haloformyl. hydroxyl, aldehyde, carboxamide, amine, amino, alkoxy, 65 azo, benzyl, carbonate ester, carboxylate, carboxyl, ketoam ine, isocyanate, isocyanide, isothiocyanate, nitrile, nitro, nitroso, phosphine, phosphate, phosphono, phosphate, US 9,708,528 B2 7 8 pyridyl, Sulfonyl, Sulfo, Sulfinyl, Sulfhydryl, halo, aryl, Sub wherein stituted aryl, heteroaryl, substituted heteroaryl or a hetero Z may be heteroatoms, such as S, SO, O, Se and NR; cyclic group. R" is an alkyl group, alkoxy group, halogen atom or Y and Y are heteroatoms, such as S, SO, O, Se and trifluoromethyl group. R is a hydrogen atom or a NR. P-E' group can be P(=O), P(=S), P(BH), P(CH), substituted or unsubstituted alkyl, aryl or cycloalkyl P(lp), P(R), P(BL), P(WL), P(CrLs), P(MnLs), P(MoLs), group. P(ReL), P(PtL), P(PdL), P(CuI), P(CuI), P(RuLs), Ring F is cyclic structure derivatives where the cyclic P(IrLs), P(FeL), P(RhIL), P(RhLs), P(CoL), P(NiL), structures are independently selected from a 5- or 6-mem bered arene, heteroacene or heterocycle known in the art. P(AgI), P(AgI), P(AuI), or P(AuL)', where lp is lone pair 10 electron and R. R' or L is independently alkyl, alkenyl, The arene, heteroacene or heterocycle can be benzene, alkylaryl, cycloalkyl, haloformyl, hydroxyl, aldehyde, car pyridine, thiophene, furan, pyrazole, imidazole, oxazole, boxamide, amine, amino, alkoxy, azo, benzyl, carbonate isoxazole, thiazole, isothiazole, isoquioline, pyrrole, pyra ester, carboxylate, carboxyl, ketoamine, isocyanate, isocya Zine, pyridazine, pyrimidine, benzimidazole, benzofuran, nide, isothiocyanate, nitrile, nitro, nitroso, phosphine, phos 15 benzothiazole, indole, naphthalene, anthracene, pyrene, tri phate, phosphono, phosphate, pyridyl, Sulfonyl, Sulfo, Sulfi azole, tetrazole, pyran, thiapyran, oxadiazole, triazine, tet nyl, sulfhydryl, halo, aryl, substituted aryl, heteroaryl, razine, carbazole, dibenzothiophene, dibenzofuran, fluorene substituted heteroaryl or a heterocyclic group, wherein the and derivatives thereof. said P-E' group is P(CH) or P(R), and wherein P(CH) or Ring F can be unsubstituted or can be substituted with one P(R') may be having a counter-anion: OTf, PF, BF, or more alkyl, alkenyl, alkynyl, alkylaryl, cycloalkyl, halo BPh, CIO or halide ions, where R' is independently formyl, hydroxyl, aldehyde, carboxamide, amine, amino, alkyl, alkenyl, alkylaryl, cycloalkyl, haloformyl, hydroxyl, alkoxy, azo, benzyl, carbonate ester, carboxylate, carboxyl, aldehyde, carboxamide, amine, amino, alkoxy, azo, benzyl, ketoamine, isocyanate, isocyanide, isothiocyanate, nitrile, carbonate ester, carboxylate, carboxyl, ketamine, isocya nitro, nitroso, phosphine, phosphate, phosphono, phosphate, nate, isocyanide, isothiocyanate, nitrile, nitro, nitroso, phos 25 pyridyl, Sulfonyl, Sulfo, Sulfinyl, Sulfhydryl, halo, aryl, Sub phine, phosphate, phosphono, phosphate, pyridyl, Sulfonyl, stituted aryl, heteroaryl, substituted heteroaryl or a hetero sulfo, sulfinyl, sulfhydryl, halo, aryl, substituted aryl, het cyclic group, and additionally, or alternatively, any two eroaryl, Substituted heteroaryl or a heterocyclic group. adjacent Substituted positions of ring F together form, inde The diarylethene-containing heterocycle derivatives of pendently, a fused 5- or 6-membered cyclic group, wherein the present invention have the formula (I) as defined above. the said cyclic group is cycloalkyl, cycloheteroalkyl, aryl, or In the present invention, the heterocyclic group for C and D heteroaryl, and wherein the fused 5- to 6-membered cyclic has the formula (II) or (III): group may be substituted with one or more of alkyl, alkenyl, alkynyl, alkylaryl, cycloalkyl, haloformyl, hydroxyl, alde 35 hyde, carboxamide, amine, amino, alkoxy, azo, benzyl, (II) carbonate ester, carboxylate, carboxyl, ketamine, isocya nate, isocyanide, isothiocyanate, nitrile, nitro, nitroso, phos phine, phosphate, phosphono, phosphate, pyridyl, Sulfonyl, R1 W >- sulfo, sulfinyl, sulfhydryl, halo, aryl, substituted aryl, het E. 40 eroaryl, Substituted heteroaryl or a heterocyclic group. Specific examples of formula (II) and (III) include the following. wherein E may be C R or N: E may be heteroatoms, such as S, SO, O, Se and NR; 45 R" is an alkyl group, alkoxy group, halogen atom or trifluoromethyl group. R and R independently represent atoms or groups selected from the group of hydrogen atom, halogen atom, hydroxyl group, alkyl group, alkynyl group, alkoxy group, cyano group, nitro group, alkylcarbonyl 50 S CHO S group, alkoxycarbonyl group, perfluoroallyl group, aryl group, cycloalkyl group, arylcarbonyl group, aryloxycarbo nyl group, diarylamino group, dialkylamino group, mono- or dialkylaminocarbonyl group, alkylcarbonyloxy group, aryl carbonyloxy group, aryloxy group, alkoxycarbonyl group, 55 and aryloxycarbonyloxy group. R' is a hydrogen atom or a Substituted or unsubstituted alkyl, aryl or cycloalkyl group. S 2

(III) 60 ) O Z 65 US 9,708,528 B2 10 -continued -continued

(CH2)CH3 / \ SeK / S \ (CH2)CH2} V-113 o S \s o, o os.10 o, 2O

soS S sors

/ \ N 50 n 21

ce 6560 US 9,708,528 B2 11 12 -continued alkoxy, azo, benzyl, carbonate ester, carboxylate, carboxyl, ketoamine, isocyanate, isocyanide, isothiocyanate, nitrile, nitro, nitroso, phosphine, phosphate, phosphono, phosphate, pyridyl, Sulfonyl, Sulfo, Sulfinyl, Sulfhydryl, halo, aryl, Sub stituted aryl, heteroaryl, substituted heteroaryl or a hetero cyclic group. O-O. The term “arylalkynyl as used herein includes an alkynyl group which has an aromatic group as a Substituent. The arylalkynyl group may be unsubstituted or substituted with 10 one or more substituents including, but not limited to, alkyl, alkenyl, alkynyl, alkyl aryl, cycloalkyl, haloformyl. hydroxyl, aldehyde, carboxamide, amine, amino, alkoxy, aZo, benzyl, carbonate ester, carboxylate, carboxyl, ketoam ine, isocyanate, isocyanide, isothiocyanate, nitrile, nitro, 15 nitroso, phosphine, phosphate, phosphono, phosphate, pyridyl, Sulfonyl, Sulfo, Sulfinyl, Sulfhydryl, halo, aryl, Sub stituted aryl, heteroaryl, substituted heteroaryl or a hetero cyclic group. The term “alkylaryl as used herein includes an alkyl group which has an aromatic group as a Substituent. The alkynyl group may be unsubstituted or Substituted with one or more Substituents including, but not limited to, alkyl, alkenyl, cycloalkyl, haloformyl, hydroxyl, aldehyde, car 25 boxamide, amine, amino, alkoxy, azo, benzyl, carbonate ester, carboxylate, carboxyl, ketoamine, isocyanate, isocya nide, isothiocyanate, nitrile, nitro, nitroso, phosphine, phos phate, phosphono, phosphate, pyridyl, Sulfonyl, Sulfo, Sulfi nyl, sulfhydryl, halo, aryl, substituted aryl, heteroaryl, 30 Substituted heteroaryl or a heterocyclic group. The term “cycloalkyl as used herein includes cyclic alkyl groups. Cycloalkyl groups can contain 3 to 7 or more carbon The term “halo' or “halogen includes a fluorine, chlo atoms and include cyclopropyl, cyclopentyl, cyclohexyl, and rine, bromine and iodine. The term “alkyl as used herein the like. Cycloalkyl groups may be unsubstituted or substi 35 tuted with one or more Substituents including, but not includes either a straight or branched chain alkyl groups. limited to, alkyl, alkenyl, alkylaryl, cycloalkyl, haloformyl. The alkyl groups contain at least one to eighteen or more hydroxyl, aldehyde, carboxamide, amine, amino, alkoxy, carbon atoms, including, but not limited to, methyl, ethyl, aZo, benzyl, carbonate ester, carboxylate, carboxyl, ketoam propyl, isopropyl, butyl, isobutyl, tert-butyl, 3-ethylhexyl ine, isocyanate, isocyanide, isothiocyanate, nitrile, nitro, and the like. In addition, the alkyl group may be unsubsti 40 nitroso, phosphine, phosphate, phosphono, phosphate, tuted or substituted with one or more substituents including pyridyl, Sulfonyl, Sulfo, Sulfinyl, Sulfhydryl, halo, aryl, Sub alkenyl, alkynyl, alkylaryl, cycloalkyl, haloformyl. stituted aryl, heteroaryl, substituted heteroaryl or a hetero hydroxyl, aldehyde, carboxamide, amine, amino, alkoxy, cyclic group. aZo, benzyl, carbonate ester, carboxylate, carboxyl, ketoam The term “alkoxy” as used herein includes linear or ine, isocyanate, isocyanide, isothiocyanate, nitrile, nitro, 45 branched alkoxy groups of one to eighteen or more carbon nitroso, phosphine, phosphate, phosphono, phosphate, atoms, and can be unsubstituted or substituted with one or pyridyl, Sulfonyl, Sulfo, Sulfinyl, Sulfhydryl, halo, aryl, Sub more Substituents including, but not limited to, alkyl, alk stituted aryl, heteroaryl, substituted heteroaryl or a hetero enyl, alkylaryl, cycloalkyl, haloformyl, hydroxyl, aldehyde, cyclic group. carboxamide, amine, amino, alkoxy, azo, benzyl, carbonate The term “alkenyl as used herein includes both straight 50 ester, carboxylate, carboxyl, ketoamine, isocyanate, isocya and branched chain alkene radicals of two to eighteen or nide, isothiocyanate, nitrile, nitro, nitroso, phosphine, phos more carbon atoms. The alkenyl group can be unsubstituted phate, phosphono, phosphate, pyridyl, Sulfonyl, Sulfo, Sulfi or substituted with one or more substituents including, but nyl, sulfhydryl, halo, aryl, substituted aryl, heteroaryl, not limited to, alkynyl, alkylaryl, cycloalkyl, haloformyl. Substituted heteroaryl or a heterocyclic group. hydroxyl, aldehyde, carboxamide, amine, amino, alkoxy, 55 Aryl alone or in combination includes carbocyclic aro aZo, benzyl, carbonate ester, carboxylate, carboxyl, ketoam matic systems containing one, two or three rings, wherein ine, isocyanate, isocyanide, isothiocyanate, nitrile, nitro, each ring may be attached together in a pendant manner or nitroso, phosphine, phosphate, phosphono, phosphate, may be fused and can be 5- or 6-membered rings. The aryl pyridyl, Sulfonyl, Sulfo, Sulfinyl, Sulfhydryl, halo, aryl, Sub rings can be unsubstituted or substituted with one or more stituted aryl, heteroaryl, substituted heteroaryl or a hetero 60 Substituents including, but not limited to, alkyl, alkenyl, cyclic group. alkylaryl, cycloalkyl, haloformyl, hydroxyl, aldehyde, car The term “alkynyl' as used herein includes both straight boxamide, amine, amino, alkoxy, azo, benzyl, carbonate and branched chain alkyne radicals of two to eighteen or ester, carboxylate, carboxyl, ketoamine, isocyanate, isocya more carbon atoms. The alkynyl group can be unsubstituted nide, isothiocyanate, nitrile, nitro, nitroso, phosphine, phos or substituted with one or more substituents including, but 65 phate, phosphono, phosphate, pyridyl, Sulfonyl, Sulfo, Sulfi not limited to, alkyl, alkenyl, alkylaryl, cycloalkyl, halo nyl, sulfhydryl, halo, aryl, substituted aryl, heteroaryl, formyl, hydroxyl, aldehyde, carboxamide, amine, amino, Substituted heteroaryl or a heterocyclic group. US 9,708,528 B2 13 14 Heteroaryl alone or in combination includes heterocyclic wherein information recording is conducted by inducing a aromatic systems which contain one, two, three or more color change when irradiated with light and the reproduction rings, wherein each ring may be combined in a pendant or of the recorded information is affected by reading the fused manner, wherein each ring of the system is a 5- or difference in the absorbance or in the reflectivity between the 6-membered rings. 5 portion where such color changes have occurred and the Heterocyclic and heterocycles refer to a 3- to 7-membered portion where no Such color change has occurred. The ring containing at least one heteroatom. The heterocyclic optical recording material can be prepared by forming a rings can be aromatic, including, but not limited to, pyridine, recording layer by any method known to those skilled in the thiophene, furan, pyrazole, imidazole, oxazole, isoxazole, art, for example by the following method: thiazole, isothiazole, isoquinoline, pyrrole, pyrazine, 10 The photochromic compound is dissolved in a solvent pyridazine, pyrimidine, benzimidazole, benzofuran, benzo Such as dichloromethane, chloroform, carbon tetrachloride, thiazole, indole, naphthalene, triazole, tetrazole, pyran, thi benzene or cyclohexane, if necessary, together with a binder apyran, oxadiazole, triazine, carbazole, dibenzothiophene, such as poly(methyl methacrylate) (PMMA), polyester dibenzofuran, indole, and fluorene. The heterocyclic rings resin, polystyrene resin, polyvinyl butyral resin or polyvi can be non-aromatic, including, but not limited to, aziridine, 15 nylidene chloride, and then, coated on a suitable Substrate oxirane, thirane, oxaziridine, dioxirane, aZetidine, oxetane, including, but not limited to, quartz plate, glass plate and thietane, diaZetidine, dioxetane, dithietane, tetrahydro plastic film by spin-coating, spray-coating, dip-coating, furane, thiolane, borolane, phospholane, arsolane, Stibolane, layer-by-layer deposition, or ink-jet printing, or vapor depo bismolane, silane, Stannolane, piperazine, piperidine, and sition. pyrrolidine. Heterocyclic rings can be unsubstituted or Sub The following examples illustrate the subject invention. stituted, which can include, but are not limited to, alkyl, Unless otherwise indicated in the following examples and alkoxy, aryl. The heteroatoms include, but not limited to, S. elsewhere in the specification and claims, all parts and O, N, Si or P. percentages are by weight, all temperatures are in degrees The present invention is illustrated by the following Centigrade, and pressure is at or near atmospheric pressure. non-limiting examples. It is to be understood that changes 25 With respect to any figure or numerical range for a given and variations can be made therein without deviating from characteristic, a figure or a parameter from one range may be the scope and the spirit of the invention as hereinafter combined with another figure or a parameter from a different claimed. It is also understood that various theories as to why range for the same characteristic to generate a numerical the invention works are not intended to be limiting. The range. compounds described herein are represented throughout by 30 Other than in the operating examples, or where otherwise their monomeric structure. As is well known to those in the indicated, all numbers, values and/or expressions referring art, the compounds may also be present as dimers, trimers, to quantities of ingredients, reaction conditions, etc., used in larger oligomers or dendrimers. the specification and claims are to be understood as modified In some embodiments, the photochromic compounds of in all instances by the term “about.” formula (I) are prepared in high purity. High purity means 35 one of at least 90% by weight pure, at least 95% by weight Example 1 pure, at least 99% by weight pure, or at least 99.9% by weight pure. The silicon- or phosphorus-containing hetero Compounds 1-5 were prepared according to the method cyclic ring structure can be prepared by any method known ology as illustrated in Scheme 1 below. Compounds 6-8 to those skilled in the art, for example the intermolecular 40 were prepared using the methodology shown in Scheme 2, coupling reaction of 2-silylaryl bromides with alkynes dis whereas compounds 9-10 were prepared according to closed in Liang, Y.; Geng, W.; Wei, J.; Xi, Z., Angew. Chem. Scheme 3 and compound 11 was prepared according to Int. Ed. 51, 1934 (2012) for preparing the silicon-containing Scheme 4. 1.2-Bis(2,5-dimethylthiophen-3-yl)ethyne was hetetocycles, the intramolecular dehydrogenative cycliza prepared in four steps from 2,5-dimethylthiophene, as tion disclosed in Kuninobu, Y.; Yoshida, T.: Takai, K.J. Org. 45 shown in Scheme 1. Then the target compounds 1-10 were Chem. 76, 7370 (2011) and the silver-mediated dehydroge prepared using similar methodology as a literature procedure native annulation disclosed in Unoh, Y.; Hirano, K. Satoh, for the intermolecular coupling reaction of 2-silylaryl bro T.: Miura, M. Angew. Chem. Int. Ed. 52, 12975 (2013) for mides with alkynes disclosed in Liang, Y.; Geng, W.; Wei, J.; the phosphorus-containing heterocycles, which are incorpo Xi, Z. Angew. Chem. Int. Ed. 51, 1934 (2012), which is rated herein by reference. The photochromic diarylethene 50 incorporated herein by reference. Compound 11 was pre functional moiety was introduced by using their correspond pared using the similar procedure as other derivatives, ing intermediates, for example 1,2-diarylethyne for the except an excess of 1.2-bis(2,5-dimethylthiophen-3-yl) intramolecular coupling reaction with 2-silylaryl bromides ethyne was used (-3 times). Compounds 12-16 were pre for the formation of silicon-containing heterocycles, cis pared according to the following methodology as illustrated diarylethene-containing hydrophosphine oxide for the intra 55 in Scheme 5 below. Compounds 17-20 were prepared using molecular dehydrogenative cyclization and 1,2-diarylethyne the methodology shown in Scheme 6, whereas compounds for the silver-mediated dehydrogenative annulation for the 21-22 were prepared according to Scheme 7. The phosphole formation of phosphorus-containing heterocycles, to yield oxides were prepared using similar methodology as a litera the target photochromic compounds. The phosphorus center ture procedure for the intramolecular dehydrogenative cycl in phosphole oxides was Subsequently functionalized by 60 ization disclosed in Kuninobu, Y.; Yoshida, T.: Takai, K. J. various chemical modifications, such as oxidation to phos Org. Chem. 76,7370 (2011), which is incorporated herein by phine oxides, Sulfides or selenides, formation of phospho reference. As indicated in Scheme 6 and Scheme 7, the nium salts, or complexation with Lewis acids or transition phosphorus center in phosphole oxides was further func metals. tionalized by various chemical modifications, for example On the other hand, described herein is an optical recording 65 the methods disclosed in Hay, C.; Fischmeister, C.; Hissler, material having Such a silole- or phosphole-containing pho M.; Toupet, L.; Réau, R. Angew. Chem., Int. Ed. 39, 1812 tochromic compound incorporated in a recording layer, (2000) and Dienes, Y.; Durben, S.; Kárpáti. T.; Neumann, T.; US 9,708,528 B2 15 16 Englert, U.; Nyulászi, L.; Baumgartner, T. Chem. Eur: J., 13, -continued 7487 (2007), which are incorporated herein by reference. Br Compounds 23-28 were prepared according to the method ology as depicted in Scheme 8. Compounds 29-32 were TMS prepared by the methodology described in Scheme 9. Com- 5 -- pounds 33 was prepared according to the methodology as shown in Scheme 10. The phosphole oxides were prepared using similar methodology as the literature procedure for the R silver-mediated dehydrogenative annulation disclosed in Unoh, Y.: Hirano, K.; Satoh, T.; Miura, M. Angew. Chem. 10 P(Bu), LiO'Bu Int. Ed. 52, 12975 (2013) and Chen, Y.-R.: Duan, W.-L.J. PdCI(T-Allyl) Am. Chem. Soc. 135, 16754 (2013), which are incorporated Toluene herein by reference. The functionalization at, the phosphorus center of the phosphole to afford compounds 29-32 was is achieved by various chemical modifications, which were disclosed by Chan, J. C.-H.; Lam, W. H.; Wong, H.-L.; Wong, W.-T: Yam. V. W.-W. Angew. Chem. Int. Ed. 52, 1 (2013), Bouit P-A.; Escande, A.; Szlics, R.: Szieberth, D.; Lescop, C.; Nyulászi, L.; Hissler, M.: Réau, R.J. Am. Chem. 20 Soc. 134, 6524 (2012) and Moussa, M. E. S.; Friess, F: Shen, W.; Hissler, M.: Réau, R.: Lescop, C. Chem. Commun. 49, 6158 (2013), which are incorporated herein by reference. The phosphole-containing metal complex 33 was prepared using similar methodology as the literature procedure 25 reported in Dienes, Y.; Eggenstsin, M.: Kárpáti. T.; Suther land, T. C.; Nyulászi, L.; Baumgartner, T. Chem. Eur: J. 14, 1; R = H 9878 (2008), which is incorporated herein by reference. 3;2: R = CNCF 4; R = OMe 30 5: R=NMe2 Scheme 1 Synthetic pathway for compounds 1-5 S I, HIO/H2O \ f " 2 cc,4 ACAoi 35 Scheme 2 Synthetic pathway for compounds 6-8 S CuI, PPh3 S TMS H PoCl2(PPh3)2 Br2 \ f -- –F– --e-'PrNH 7 CHCI e

I 40 S Br BuLi, THF / CISR, THF

Br 45

-asK2CO3 / SiR3 THF, MeOH

50 Br

-- S 55 SR -- CuI, PPh3 / 3 S PdCl2(PPh3)2 \ f -->'PrNH Br

I 60

P(Bu), LiO'Bu PdCl(J-Allyl) -e- Toluene 65

US 9,708,528 B2 25 26 -continued -continued

15 22

1. BuLi, THF 2. PhPCl Her 3. HO, EtN 2O Scheme 8 Synthetic pathway for compounds 23-28

Pd(OAc) - T - 45 23-24

R1 =

50 23

R = OMe

24 55 PrOH + PPhCl 1. Pyridine, toluene 2. H2O O\/ H o1 -- Lawesson reagent 60 He Toluene S

F ---- W D ---1. BuLi, EtO 65 : Ar 2. H2O

US 9,708,528 B2 29 30 -continued -continued O H s \/P

NPh Ag2O DMF

15 28

Scheme 9 Synthetic pathway for compounds 29-32

HSiCl3 Se powder -- --- Toluene THF

Laweeson reagent MeOTf -e- Toluene CHCl2 23

30 32 Scheme 10 Synthetic pathway for compound 33

Au(tht)Cl -> DCM

19 33

US 9,708,528 B2 37 38 The solution sample was irradiated at the UV absorption TABLE 1-continued band, whereby the initial colorless to pale yellow solution turned into deep-colored solution. The colored state was Electronic absorption data for the compounds in benzene solution thermally very stable. Then, it was irradiated with visible at 298K light, whereby the solution was decolorized. The UV-vis 5 Absorption absorbance changes of the compounds were capable of Compound Configuration /nm (e/dmmol 'cm) undergoing repeated reversible changes. FIG. 1 shows the 23 Open form 360 (5560) UV-vis absorption spectral changes of 1 in degassed benzene Closed form 357 (31900), 499 (5050) upon excitation at 362 nm. FIG. 2 shows the photochromic 25 Open form 333 (8090), 408 (7030) reaction of compound 12 and FIG. 3 shows the UV-vis 10 Closed form 357sh (31800), 371 (47.600), 486 (5910) absorption spectral changes of 12 in degassed benzene upon 31 Open form 354 (7700) Closed form 360 (26700), 502 (3730) excitation at 391 nm. FIG. 4 show the UV-vis absorption 32 Open form 358 (6520) spectral changes of 23 in degassed benzene upon excitation Closed form 360 (30300), 381 (25700), 448 (5850), at 360 nm. FIG. 5 show the UV-vis absorption spectral 519 (4960) 15 33 Open form 317 (9750), 362 (10400) changes of 33 in degassed benzene upon excitation at 360 Closed form 367 (34500), 458 (4560), 608 (12700) nm. The electronic absorption data of the open forms and 367 (34500), 458 (4560), 608 (12700) closed forms are summarized in Table 1. Besides the UV-vis spectral change, the emission intensity would decrease upon photocyclization of the phosphole compounds (FIG. 6), rendering the compounds possible photoSwitchable materi TABLE 2 als. The quantum yields for both photocyclization and Photochemical quantum yields and conversion at photostationary state photo-cycloreversion of the photochromic compounds are determined in degassed benzene solution at 298K Summarized in Table 2. The conversion at photostationary state is also Summarized in Table 2. Photochemical Quantum Yield/d Conversion at 25 Compound Photocyclization Photocycloreversion PSS (%) TABLE 1. 1 0.39 O.27 44 Electronic absorption data for the compounds in benzene solution 4 O.32 0.31 44 at 298K 6 0.19 0.20 53 8 0.48 O42 66 Absorption 30 9 0.42 0.36 67 Compound Configuration /nm (e/dmmol 'cm) 11 O.32 0.19 8O 12 0.28 0.03° 49 1 Open form 330 (6470) 13 0.45 0.023 87 Closed form 332sh (22200), 342 (26250), 475 (4490) 14 O.23 0.014 60 4 Open form 296 (8680), 343 (5530) 15 O.50 O.0576 62 Closed form 340 (27760), 477 (4000) 35 16 0.37b 0.063 63 6 Open form 360 (5220) 17 0.37b 0.026 69 Closed form 342 (24600), 444 (5600) 18 0.34 O.0276 46 8 Open form 334 (6470), 371 (8820) 19 0.43 0.0216 53 Closed form 343 (25800), 359 (38790), 474 (4470) 2O 0.17b 0.048 37 9 Open form 299 (25160), 350sh (4620), 378sh (2470) 21 0.26 O.097 39 Closed form 319 (24400), 341sh (20660), 440 (3860) 40 22 0.08 0.092 85 1 Open form 308 (10640), 318 (10640), 333 (9240), 23 0.64 O.24 34 385 (17820) 25 0.52 0.21e 83 Closed form 352 (29070), 371 (34630), 472 (7210), 31 0.65 0.298 59 498sh (6100) 32 O.20 0.074 49 2 Open form 324 (8870), 365 (98.60) 33 0.18 O.O16 38 Closed form 288 (19870), 363 (29750), 426 (3790), 600 (9390) 45 Data obtained with an uncertainty of +10% 3 Open form 308 (6750), 378 (9050) TData obtained using 334 nm as the excitation source Closed form 294 (16250), 369 (18000), 477 (2810), TData obtained using 468 nm as the excitation source 629 (5010) Data obtained using 509 mm as the excitation source 4 Open form 325 (8380), 376 (10850) TData obtained using 500 nm as the excitation source Closed form 292 (21450), 372 (25900), 470 (4390), 623 (8250) 50 5 Open form 327 (6690), 366 (6790) Example 2 Closed form 288 (10140), 364 (16700), 460 (1740), 587 (4550) Compound 12 was used to demonstrate the thermal sta 6 Open form 333 (10630), 376 (7970) Closed form 288 (10780), 369 (23910), 459 (2110), bility of the closed form of the photochromic compounds by 582 (5390) 55 measuring the absorbance decay at different temperatures in 7 Open form 304 (12990), 364 (9780) the dark (FIG. 7). Compound 25 was also selected to Closed form 365 (23900), 457 (31.80), 602 (8390) investigate the thermal stability at 358 K (FIG. 8). By 8 Open form 321 (7160), 351 (9050) Closed form 361 (22970), 592 (94.40) plotting the rates of thermal backward reaction at different 9 Open form 328 (12100) temperature against the temperature, the Arrhenius plot Closed form 357 (24000), 573 (9170) (FIG. 9) could be obtained, which could be used to deter 2O Open form 310 (4580), 376 (4200) 60 mine the activation energy (120.6 kJ mol') and the pre Closed form 295 (11433), 371 (13180), 460 (2200), 631 (3830) exponential factor (1.01x10's") of the thermal cyclorever 21 Open form 324 (10180), 363 (6950) sion of compound 12. Closed form 314 (12080), 357 (15690), 559 (5910) 22 Open form 314 (19120), 382 (15660) Example 3 Closed form 316 (17350), 376 (19900), 453sh (2750), 65 572sh (3410), 591 (3540) Fatigue resistance represents another important parameter commonly used to evaluate the performance of photochro US 9,708,528 B2 39 40 mic materials. Photochromic materials could lose their pho nyl, sulfhydryl, halo, aryl, substituted aryl, heteroaryl, tochromic reactivities though side-reactions of the closed Substituted heteroaryl or a heterocyclic group. form. The fatigue resistance of the compound could be 3. The photochromic compound according to claim 2, demonstrated by alternate excitation at the absorption bands wherein the X is P(CH)R or P(R')R, and wherein P(CH)R of the open form and the closed form of the compounds and 5 or P(R')R have a counter-anion: OTf, PF, BF, BPha, monitoring the UV-vis absorption changes at a selected CIO or halide ions, where R and R' are independently wavelength. Compound 6 and 23 were used to demonstrate alkyl, alkenyl, alkylaryl, cycloalkyl, haloformyl, hydroxyl, the fatigue resistance of the photochromic compounds, as aldehyde, carboxamide, amine, amino, alkoxy, azo, benzyl, depicted in FIGS. 10 and 11, respectively. carbonate ester, carboxylate, carboxyl, ketoamine, isocya 10 nate, isocyanide, isothiocyanate, nitrile, nitro, nitroso, phos Example 4 phine, phosphate, phosphono, phosphate, pyridyl, Sulfonyl, sulfo, sulfinyl, sulfhydryl, halo, aryl, substituted aryl, het Photochromic properties of compounds 2 and 12 in solid eroaryl, Substituted heteroaryl or a heterocyclic group. thin film were studied by dissolving 80 mg of PMMA and 4. The photochromic compound according to claim 1, the compound (25 mg of 2 or 15 mg of 12) into 1 mL of 15 wherein rings A and B are cyclic structure derivatives where chloroform. Then it was spin-coated on a quartz plate (20 the cyclic structures are independently selected from a 5- or mmx20mm x1 mm) with a spin rotation speed of 2000 rpm 6-membered arene, heteroacene or heterocycle, the arene, on a Laurell Technologies Corporation Single Wafer Spin heteroacene or heterocycle selected from benzene, pyridine, Processor (Model: WS-400A6TFM/LITE). With the use of thiophene, furan, pyrazole, imidazole, oxazole, isoxazole, a mask, the quartz plate is able to be recorded with different thiazole, isothiazole, isoquioline, pyrrole, pyrazine, patterns by undergoing a color change and it is stable in the pyridazine, pyrimidine, benzimidazole, benzofuran, benzo dark for a period of time. thiazole, indole, naphthalene, anthracene, pyrene, triazole, Those skilled in the art will recognize that various tetrazole, pyran, thiapyran, oxadiazole, triazine, tetrazine, changes and modifications can be made in the invention carbazole, dibenzothiophene, dibenzofuran, fluorene, or without departing from the spirit and scope thereof. The 25 derivatives thereof. various embodiments described were for the purpose of 5. The photochromic compound according to claim 1, further illustrating the invention and were not intended to wherein rings A and B are unsubstituted or substituted with limit it. one or more alkyl, alkenyl, alkynyl, alkylaryl, cycloalkyl, What is claimed is: haloformyl, hydroxyl, aldehyde, carboxamide, amine, 1. A photochromic compound comprising a diarylethene, 30 amino, alkoxy, azo, benzyl, carbonate ester, carboxylate, in which an ethene moiety forms part of a mono- or carboxyl, ketoamine, isocyanate, isocyanide, isothiocyanate, poly-cyclic ring structure with at least one of a silicon nitrile, nitro, nitroso, phosphine, phosphate, phosphono, containing heterocycle or a phosphorus-containing hetero phosphate, pyridyl, Sulfonyl, Sulfo, Sulfinyl, Sulfhydryl, halo, cycle, which comprises a butadiene or a hexatriene moiety aryl, substituted aryl, heteroaryl, substituted heteroaryl or a to form a conjugated aromatic heterocycle, the photochro 35 heterocyclic group, and additionally, or alternatively, any mic compound having the chemical structure two adjacent Substituted positions of rings A and B together form, independently, a fused 5- or 6-membered cyclic group, wherein the said cyclic group is cycloalkyl, cyclohet eroalkyl, aryl, or heteroaryl, and wherein the fused 5- to C 40 6-membered cyclic group is substituted with one or more of alkyl, alkenyl, alkynyl, alkylaryl, cycloalkyl, haloformyl. hydroxyl, aldehyde, carboxamide, amine, amino, alkoxy, iii. GSO1.X pi D aZo, benzyl, carbonate ester, carboxylate, carboxyl, ket amine, isocyanate, isocyanide, isothiocyanate, nitrile, nitro, 45 nitroso, phosphine, phosphate, phosphono, phosphate, wherein: pyridyl, Sulfonyl, Sulfo, Sulfinyl, Sulfhydryl, halo, aryl, Sub X comprises silicon or phosphorus: stituted aryl, heteroaryl, substituted heteroaryl or a hetero A and B are cyclic structure derivatives, mand n are the cyclic group. number of rings in the cyclic structure derivatives 6. The photochromic compound according to claim 1, and m and n are independently greater than or equal 50 wherein the heterocyclic group for C and D in the formula to Zero; C and D are heterocyclic groups that are cyclizable by (I), has the formula (II) or (III): irradiation with light to form a cyclohexadiene ring for tuning the optical properties. (II) 2. The photochromic compound according to claim 1, 55 wherein X is one or more of SiRR', P(O)R, P(BH)R, P(BL)R, P(S)R, P(Se)R, P(CH) R, P(SR)R, PR, P(R)R, P(WLs)R, P(CrLs)R, P(MnLs)R, P(MoLs)R, P(ReLs)R, R1 / >- P(PtL)R, P(PdL)R, P(CuIL)R, P(CuIL)R, P(RuL)R, E. P(IrLs)R, P(FeL)R, P(RhL)R, P(RhLs)R, P(CoL)R, 60 P(NiL)R, P(AgI)R, P(AgI)R, P(AuL)R, or P(AuD)R’ wherein where R, R or L is independently alkyl, alkenyl, alkynyl, E is C, R or N: alkylaryl, cycloalkyl, haloformyl, hydroxyl, aldehyde, car E" comprises at least one heteroatom, selected from S. boxamide, amine, amino, alkoxy, azo, benzyl, carbonate SO, O, Se and NR; ester, carboxylate, carboxyl, ketoamine, isocyanate, isocya 65 R" is an alkyl group, alkoxy group, halogen atom or nide, isothiocyanate, nitrile, nitro, nitroso, phosphine, phos trifluoromethyl group, R and R are each indepen phate, phosphono, phosphate, pyridyl, Sulfonyl, Sulfo, Sulfi dently an atom or group selected from the group of US 9,708,528 B2 41 42 hydrogen atom, halogen atom, hydroxyl group, alkyl group, alkynyl group, alkoxy group, cyano group, nitro group, alkylcarbonyl group, alkoxycarbonyl group, perfluoroalkyl group, aryl group, cycloalkyl group, arylcarbonyl group, aryloxycarbonyl group, 5 diarylamino group, dialkylamino group, mono- or dialkylaminocarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, aryloxy group, alkoxycarbonyl group, and aryloxycarbonyloxy group, and R is a hydrogen atom or a substituted or 10 unsubstituted alkyl, aryl or cycloalkyl group;

(III) 15 wherein: / \ F G and H are cyclic structure derivatives: RI Z m and n are the number of rings in the cyclic structure 2O derivatives and they are greater than or equal to Zero; wherein: X comprises silicon or phosphorus: Z comprises at least one heteroatom; and C. and f independently represent C R or N: R" is an alkyl group, alkoxy group, halogen atom or Y and W independently comprise heteroatoms selected trifluoromethyl group, R" is a hydrogen atom or a 25 from S, SO, O, Se and NR': buted or unsubstituted alkyl, aryl or cycloalkyl Rand R7 independently represent alkyl group, alkoxy Ring F comprises cyclic structure derivatives where the group, halogen atom or trifluoromethyl group; cyclic structures are independently selected from a 5- R. R. and R are independently atoms or groups or 6-membered arene, heteroacene or heterocycle, so selected from the group of hydrogen atom, halogen the arene, heteroacene or heterocycle being one or atom, hydroxyl group, alkyl group, alkynyl group, more selected from benzene, pyridine, thiophene, alkoxy group, cyano group, nitro group, alkylcarbo furan, pyrazole, imidazole, oxazole, isoxazole, thi- nyl group, alkoxycarbonyl group, perfluoroalkyl azole, isothiazole, isoquioline, pyrrole, pyrazine, group, aryl group, cycloalkyl group, arylcarbonyl pyridazine, pyrimidine, benzimidazole, benzofuran, 35 group. aryloxycarbonyl group, diarylamino grOup, benzothiazole, indole, naphthalene, anthracene, dialkylamino group, mono- or dialkylaminocarbonyl pyrene, triazole, tetrazole, pyran, thiapyran, oxadi- group, alkylcaronyloxy group, arylcarbonyloxy azole, triazine, tetrazine, carbazole, dibenzothio- group, aryloxy group, alkoxycarbonyl group, and phene, dibenzofuran, fluorene and derivatives aryloxycarbonyloxy group; and thereof; 40 R" is a hydrogenatom or a substituted or unsubstituted wherein alkyl, aryl or cycloalkyl group. Ring F can be unsubstituted or substituted with one or more alkyl, alkenyl, alkynyl, alkylaryl, cycloalkyl, 8. A photochromic compound selected from one of haloformyl, hydroxyl, aldehyde, carboxamide,

amine, amino, alkoxy, azo, benzyl, carbonate ester, 45 carboxylate, carboxyl, ketoamine, isocyanate, iso- R" C cyanide, isothiocyanate, nitrile, nitro, nitroso, phos phine, phosphate, phosphono, pyridyl, Sulfonyl, sulfo, sulfinyl, sulfhydryl, halo, aryl, substituted aryl, / \ heteroaryl, substituted heteroaryl or a heterocyclic 50 R" Si D group, and additionally, or alternatively, any two / \ adjacent Substituted positions of ring F together form, independently, a fused 5- or 6-membered C cyclic group, wherein the said cyclic group is e R" Y cycloalkyl, cycloheteroalkyl, aryl, or heteroaryl, and 55 wherein the fused 5- to 6-membered cyclic group N may be substituted with one or more of alkyl, alk enyl, alkynyl, alkylaryl, cycloalkyl, haloformyl. hydroxyl, aldehyde, carboxamide, amine, amino, alkoxy, azo, benzyl, carbonate ester, carboxylate, 60 carboxyl, ketamine, isocyanate, isocyanide, isothio cyanate, nitrile, nitro, nitroso, phosphine, phosphate, phosphono, pyridyl, Sulfonyl, Sulfo, Sulfinyl, Sulfhy dryl, halo, aryl, substituted aryl, heteroaryl, substi tuted heteroaryl or a heterocyclic group. 65 7. The photochromic compound of claim 1, wherein the compound has the chemical structure: US 9,708,528 B2 43 44 -continued -continued

wherein 35 C and D are heterocyclic groups that are cyclizable by irradiation with light to form cyclohexadiene ring for tuning the optical properties, wherein C and D have the formula (IV) or (V): 40 (IV) / E 45 R1 > R2

wherein 50 E is C R or N: E" comprises at least one heteroatom, selected from 8. SO, O, Se and NR; R" is an alkyl group, alkoxy group, halogen atom or trifluoromethyl group, R and Rare independently 55 an atoms or groups selected from the group of hydrogen atom, halogen atom, hydroxyl group, alkyl group, alkynyl group, alkoxy group, cyano group, nitro group, alkylcarbonyl group, alkoxycarbonyl 60 group, perfluoroalkyl group, aryl group, cycloalkyl group, arylcarbonyl group, aryloxycarbonyl group, diarylamino group, dialkylamino group, mono- or dialkylaminocarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, aryloxy group, 65 alkoxycarbonyl group, and aryloxycarbonyloxy group, and R is a hydrogen atom or a substituted or unsubstituted alkyl, aryl or cycloalkyl group; US 9,708,528 B2 45 46 L is independently alkyl, alkenyl, alkynyl, alkylaryl, (V) cycloalkyl, haloformyl, hydroxyl, aldehyde, carbox amide, amine, amino, alkoxy, azo, benzyl, carbonate ester, carboxylate, carboxyl, ketoamine, isocyanate, isocyanide, isothiocyanate, nitrile, nitro, nitroso, RI Z phosphine, phosphate, phosphono, pyridyl, Sulfonyl, sulfo, sulfinyl, sulfhydryl, halo, aryl, substituted aryl, wherein: heteroaryl, substituted heteroaryl or a heterocyclic group; Z comprises at least one heteroatom selected from S. 10 SO, O, Se and NR; Y and Y are independently selected from CR, S, SO, R" is an alkyl group, alkoxy group, halogen atom or O, Se and NR", where R is an atom or group selected trifluoromethyl group, R is a hydrogen atom or a from the group of hydrogen atom, halogen atom, substituted or unsubstituted alkyl, aryl or cycloalkyl hydroxyl group, alkyl group, alkynyl group, alkoxy group; 15 group, cyano group, nitro group, alkylcarbonyl Ring F comprises cyclic structure derivatives where the group, alkoxycarbonyl group, perfluoroalkyl group, cyclic structures are independently selected from a 5 aryl group, cycloalkyl group, arylcarbonyl group, or 6-membered arene, heteroacene or heterocycle, aryloxycarbonyl group, diarylamino group, dialky the arene, heteroacene or heterocycle being one or lamino group, mono- or dialkylaminocarbonyl more selected from benzene, pyridine, thiophene, group, alkylcaronyloxy group, arylcarbonyloxy furan, pyrazole, imidazole, oxazole, isoxazole, thi group, aryloxy group, alkoxycarbonyl group, and azole, isothiazole, isoquioline, pyrrole, pyrazine, aryloxycarbonyloxy group, and R is a hydrogen pyridazine, pyrimidine, benzimidazole, benzofuran, atom or a substituted or unsubstituted alkyl, aryl or benzothiazole, indole, naphthalene, anthracene, cycloalkyl group. pyrene, triazole, tetrazole, pyran, thiapyran, oxadi 25 9. A method of making a photochromic compound com azole, triazine, tetrazine, carbazole, dibenzothio prising a diarylethene, in which an ethene moiety forms part phene, dibenzofuran, fluorene and derivatives of a mono- or poly-cyclic ring structure with at least one of thereof, and a silicon-containing heterocycle or a phosphorus-containing Ring F can be unsubstituted or can be substituted with heterocycle, comprising: one or more alkyl, alkenyl, alkynyl, alkylaryl, 30 a) performing an intermolecular coupling reaction of a cycloalkyl, haloformyl, hydroxyl, aldehyde, carbox 2-silylaryl bromide with an alkyne to provide the amide, amine, amino, alkoxy, azo, benzyl, carbonate silicon-containing heterocycle comprising a photochro ester, carboxylate, carboxyl, ketoamine, isocyanate, mic diarylethene functional moiety, or isocyanide, isothiocyanate, nitrile, nitro, nitroso, b) performing an intramolecular dehydrogenative cycl phosphine, phosphate, phosphono, pyridyl, Sulfonyl, 35 ization with a photochromic diarylethene functional sulfo, sulfinyl, sulfhydryl, halo, aryl, substituted aryl, ized intermediate to provide the phosphorus-containing heteroaryl, substituted heteroaryl or a heterocyclic heterocycle comprising a photochromic diarylethene group, and additionally, or alternatively, any two functional moiety, or adjacent Substituted positions of ring F together c) performing a silver-mediated dehydrogenative annula form, independently, a fused 5- or 6-membered 40 tion with an alkyne to provide a phosphorus-containing cyclic group, wherein the said cyclic group is heterocycle comprising a photochromic diarylethene cycloalkyl, cycloheteroalkyl, aryl, or heteroaryl, and functional moiety. wherein the fused 5- to 6-membered cyclic group 10. The method of claim 9, whereina) is performed and may be substituted with one or more of alkyl, alk the alkyne comprises 1,2-diarylethyne. enyl, alkynyl, alkylaryl, cycloalkyl, haloformyl. 45 11. The method of claim 9, wherein b) is performed and hydroxyl, aldehyde, carboxamide, amine, amino, the photochromic diarylethene functional moiety interme alkoxy, azo, benzyl, carbonate ester, carboxylate, diate comprises cis-diarylethene-containing hydrophosphine carboxyl, ketamine, isocyanate, isocyanide, isothio oxide. cyanate, nitrile, nitro, nitroso, phosphine, phosphate, 12. The method of claim 9, wherein c) is performed and phosphono, pyridyl, Sulfonyl, Sulfo, Sulfinyl, Sulfhy 50 the alkyne comprises 1,2-diarylethyne. dryl, halo, aryl, substituted aryl, heteroaryl, substi 13. The method of claim 9, whereb) is performed and the tuted heteroaryl or a heterocyclic group; method further comprises functionalizing the phosphorus by R. R', R" are independently atoms or groups selected one of: from the group of hydrogen atom, halogen atom, oxidation to phosphine oxides, Sulfides or selenides; hydroxyl group, alkyl group, alkynyl group, alkoxy 55 formation of phosphonium salts; or group, cyano group, nitro group, alkylcarbonyl complexation with Lewis acids or transition metals. group, alkoxycarbonyl group, perfluoroalkyl group, 14. The method of claim 9, where c) is performed and the aryl group, cycloalkyl group, arylcarbonyl group, method further comprises functionalizing the phosphorus by aryloxycarbonyl group, diarylamino group, dialky one of: lamino group, mono- or dialkylaminocarbonyl 60 oxidation to phosphine oxides, Sulfides or selenides; group, alkylcaronyloxy group, arylcarbonyloxy formation of phosphonium salts; or group, aryloxy group, alkoxycarbonyl group, and complexation with Lewis acids or transition metals. aryloxycarbonyloxy group; 15. A photochromic device comprising a layer comprising E" refers to atoms or groups selected from O, BH, the photochromic compound of claim 1 in a photochromic BL, S. Se, CH, SR, R., WLs, CrLs, MnLs, MoLs, 65 layer. ReLs, Pts, PdL. CuI, Cul, RuLs IrLs FeLa Rhs, 16. The photochromic device according to claim 15, RhLs, CoL. NiL, AgI, AgI or Aull where R or wherein the layer comprising the photochromic compound is US 9,708,528 B2 47 48 prepared by spin-coating, spray-coating, dip-coating, layer by-layer deposition, or ink-jet printing, or vapor deposition. 17. The photochromic device according to claim 15, wherein the device is coated on a suitable substrate com prising quartz plate, glass plate or plastic film. 5

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