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

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(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 A 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.
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