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Synthesis and Characterization of Bis[1]Benzothieno[3,2-B:20,30-D]Pyrroles: Quantitative Effects of Benzannulation on Dithieno[3,2-B:20,30-D]Pyrroles

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Synthesis and Characterization of Bis[1]Benzothieno[3,2-B:20,30-D]Pyrroles: Quantitative Effects of Benzannulation on Dithieno[3,2-B:20,30-D]Pyrroles molecules Article Synthesis and Characterization of Bis[1]benzothieno[3,2-b:20,30-d]pyrroles: Quantitative Effects of Benzannulation on Dithieno[3,2-b:20,30-d]pyrroles Rylan M. W. Wolfe , Evan W. Culver and Seth C. Rasmussen * Department of Chemistry and Biochemistry, North Dakota State University, NDSU Dept. 2735, P.O. Box 6050, Fargo, ND 58108-6050, USA; [email protected] (R.M.W.W.); [email protected] (E.W.C.) * Correspondence: [email protected]; Tel.: +1-701-231-8747 Received: 14 August 2018; Accepted: 3 September 2018; Published: 6 September 2018 Abstract: The synthesis of four N-functionalized bis[1]benzothieno[3,2-b:20,30-d]pyrroles (BBTPs) is reported in order to provide a more detailed characterization of these fused-ring units, as well as increase the scope of known BBTP units available for application to conjugated materials. The optical, electronic, and structural properties of the resulting BBTP units have been compared to the parent N-alkyl- and N-aryl-dithieno[3,2-b:20,30-d]pyrroles (DTPs), as well as their corresponding 2,6-diphenyl derivatives, in order to fully quantify the relative electronic effects resulting from benzannulation of the parent DTP building block. Such comparative analysis reveals that benzannulation results in a red-shifted absorbance, but to a lesser extent than simple phenyl-capping of the DTP. More surprising is that benzannulation results in stabilization of the BBTP HOMO, compared to the destabilization normally observed with extending the conjugation length of the backbone. Keywords: fused-ring thiophenes; heteroacenes; dithieno[3,2-b:20,30-d]pyrroles; benzannulation; structure-function relationships 1. Introduction Conjugated organic systems can provide materials that exhibit the electronic and optical properties of inorganic semiconductors, while retaining various attractive properties typically associated with organic plastics, including mechanical flexibility and low costs for production [1–3]. While such organic semiconductors are typically viewed as very modern materials, the study of these polymers dates as far back as the early 19th century [4–6], although significant interest did not arise until the first reports of their conductive nature in the early 1960s [6–10]. Since that point, the continuing academic and technological interest in these materials has given rise to the current field of organic electronics. Such development of technological applications has focused on organic photovoltaics (OPVs), field effect transistors (FETs), organic light-emitting diodes (OLEDs), electrochromic devices, and sensors [1–3]. One of the powerful aspects of these materials has been the ability to tune their electronic and optical properties at the molecular level via synthetic modification. This is especially true for thiophene-based materials, in which the ease and versatility of form via synthetic manipulation has made them especially popular [2,3]. A particularly popular approach for the synthetic modification of thiophene-based materials has been the application of fused-ring building blocks, especially the various fused 2,20-bithiophenes shown in Figure1a, including cyclopenta[2,1-b:3,4-b’]dithiophene (CDT) [2,3,11–13], silolo[3,2-b:4,5-b’]dithiophene (SDT) [3,11,12], dithieno[3,2-b:20,30-d]pyrrole (DTP) [2,3,11–16], phospholo[3,2-b:4,5-b’]dithiophene (PDT) [3,11,12], germolo[3,2-b:4,5-b’]dithiophene (GTP) [3,17–19], and arsolo[3,2-b:4,5-b’]dithiophene (ADT) [20–22]. Molecules 2018, 23, 2279; doi:10.3390/molecules23092279 www.mdpi.com/journal/molecules Molecules 2018, 23, x 2 of 14 Molecules 2018, 23, 2279 2 of 14 [2,3,11–16], phospholo[3,2‐b:4,5‐b’]dithiophene (PDT) [3,11,12], germolo[3,2‐b:4,5‐b’]dithiophene (GTP) [3,17–19], and arsolo[3,2‐b:4,5‐b’]dithiophene (ADT) [20–22]. The fused‐ring nature of these compoundsThe fused-ring provides nature a rigid, of these planar compounds ground state, provides which can a rigid, lead planarto improved ground conjugation, state, which increased can lead delocalization,to improved conjugation,and decreased increased energy delocalization,gaps, while also and reducing decreased interannular energy gaps, torsional while also vibrations, reducing thusinterannular contributing torsional to increased vibrations, emission thus contributingquantum yields. to increased In addition, emission the bridging quantum unit yields. (ER Inor addition, ER2 in Figurethe bridging 1a) can unitcontribute (ER or ERvia2 inductivein Figure1 effectsa) can contributeto tune the via corresponding inductive effects HOMO to tune or LUMO the corresponding energies, whileHOMO the orcentral LUMO placement energies, whileof the the side central chains placement allows the of the use side of chainsfairly bulky allows groups the use without of fairly bulkythe introductiongroups without of unwanted the introduction steric interactions of unwanted that steric can interactions lead to reduced that can backbone lead to reducedplanarity backbone in the resultingplanarity materials in the resulting [12,13]. materials [12,13]. (a) (b) FigureFigure 1. 1.(a)( aFused) Fused 2,2 2,2′‐bithiophene0-bithiophene building building blocks; blocks; (b) ( bVarious) Various extended extended fused fused-ring‐ring analogues analogues of of dithieno[3,2dithieno[3,2-‐b:2b′:2,30′‐,3d0]pyrrole-d]pyrrole (DTP). (DTP). MoreMore recently, recently, variousvarious groups groups have have begun begun investigating investigating analogous analogous building blocksbuilding incorporating blocks incorporatingfurther annulated further rings. annulated This is rings. especially This trueis especially for the popular true for DTP the units,popular for DTP which units, a number for which of such a numberextended of analoguessuch extended have analogues been reported have (Figure been 1reportedb) [ 23–32 (Figure]. Of these 1b) extended [23–32]. analogues,Of these extended the oldest 0 0 analogues,and most the simple oldest are and the most bis[1]benzothieno[3,2- simple are the bis[1]benzothieno[3,2b:2 ,3 -d]pyrroles (BBTPs),‐b:2′,3′‐d which]pyrroles were (BBTPs), first introduced which wereby Liu first in introduced 2008 [23]. In by the Liu following in 2008 [23]. decade, In the additional following reports decade, of BBTPs additional have appearedreports of [ 24BBTPs–27], buthave the appearedscope of [24–27], these building but the blocks scope isof still these somewhat building limited, blocks is with still only somewhat a total oflimited, seven with members only reporteda total ofto seven date. members It should reported be pointed to out date. that It theshould nomenclature be pointed used out tothat refer the to nomenclature these units changes used to from refer paper to theseto paper, units changes none of whichfrom paper correspond to paper, to none the correct of which and correspond proper IUPAC to the or correct CAS nomenclature. and proper IUPAC This is orperhaps CAS nomenclature. not surprising This as is the perhaps nomenclature not surprising of such as the complicated nomenclature species of such is rarely complicated covered species in even is graduaterarely covered coursework, in even such graduate that most coursework, in the field such are that not most very in familiar the field with are the not subtleties very familiar of correctly with thenaming subtleties fused-ring of correctly systems. naming In order fused to assist‐ring the systems. field with In such order complexities, to assist anthe educational field with guide such to complexities,fused-ring nomenclature an educational has guide been to recently fused‐ring published nomenclature [33]. has been recently published [33]. AlthoughAlthough BBTPs BBTPs have have been been studied studied as as both both molecular molecular materials materials [23,24] [23,24 and] and incorporated incorporated into into polymericpolymeric materials materials [26,34], [26,34 ],only only four four BBTPs BBTPs have have currently currently been been characterized characterized in interms terms of of their their opticaloptical and and electronic electronic properties properties [23,24]. [23,24 ].Perhaps Perhaps more more critically, critically, at atno no point point have have the the resulting resulting propertiesproperties of of BBTPs BBTPs been been directly directly compared compared to to the the parent parent DTPs, DTPs, although although some some limited limited attempts attempts to to comparecompare analogous analogous polymeric polymeric materials materials have have been been reported reported [23]. [23 ].In In order order to to provide provide a more a more detailed detailed characterizationcharacterization of ofthese these fused fused-ring‐ring units, units, as as well well as as increase increase the the scope scope of of BBTPs, BBTPs, the the synthesis synthesis and and characterizationcharacterization of offour four N N-substituted‐substituted BBTPs BBTPs are are reported reported herein. herein. Of Of these these four four BBTPs, BBTPs, three three are are previouslypreviously unreported, unreported, and and one one is isonly only the the second second example example of ofan an N‐NarylBBTP.-arylBBTP. Lastly, Lastly, the the optical, optical, electronic,electronic, and and structural structural properties properties of of the the BBTP BBTP units units have have been been compared compared to to the the parent parent N‐Nalkyl-alkyl-‐ and and N‐Naryl-aryl-DTPs,‐DTPs, as as well well as as their their corresponding corresponding 2,6 2,6-diphenyl‐diphenyl derivatives, derivatives, in inorder order to to fully fully quantify quantify the the relativerelative electronic electronic effects effects resulting resulting from from benzannulation benzannulation of of the the parent parent DTP DTP building building block. block. Molecules 2018, 23, 2279 3 of 14 Molecules 2018, 23, x 3 of 14 Molecules 2018, 23, x 3 of 14 2. Results2. Results and and Discussion Discussion 2. Results and Discussion 2.1. Synthesis2.1. Synthesis 2.1. Synthesis To date,To date, several several different different approaches approaches have have been been utilized utilized forfor the synthesis of of BBTPs, BBTPs, as as outlined outlined in Schemein 1.SchemeTo Although date, several1.
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