Nonsymmetrical Dithienylethenes Bearing Dithieno[3,2‐b:2′,3′‐d]thiophene Units with Photochromic Performance in the Crystalline Phase

Abstract

Four novel nonsymmetrical photochromic diarylethene compounds containing dithieno[3,2-b:2',3'-d]thiophene units were designed and synthesized to investigate their photochromic properties. All these molecules adopt a photoactive antiparallel conformation in single crystals, as revealed by X-ray crystallographic analysis, and exhibit excellent photochromism in solution as well as in the crystalline phase.

Dithienothiophenes at Work: Access to Mechanosensitive Fluorescent Probes, Chalcogen-Bonding Catalysis, and Beyond

“…223−225 The best results were obtained with 263: 71% yield for the photocyclization, red-shifted absorption of product 264 at 510 nm, and the lowest among the high LUMO energies at −3.71 eV. 223 Moving the aromatic extension from the diarylethene in 263 to the DTT side in 265 and twisting it a bit more reduces all these record values slightly. Moving the aromatic extension in between diarylethene and DTT at constant twist in 266 gives red-shifted cyclization products at lower yield of 53%.…”

“…With diarylethenes, the photochromic transformation is the electrocyclization of formal 1,3,5-hexatrienes 263 into formal cyclohexadienes 264 . The integration of DTTs into diarylethenes is of interest to create p semiconductors with photoswitchable transport properties. − The best results were obtained with 263 : 71% yield for the photocyclization, red-shifted absorption of product 264 at 510 nm, and the lowest among the high LUMO energies at −3.71 eV . Moving the aromatic extension from the diarylethene in 263 to the DTT side in 265 and twisting it a bit more reduces all these record values slightly.…”

D-π-D chromophores based on dithieno[3,2-b:2',3'-d]thiophene (DTT): Potential application in the fabrication of solar cell

“…[27][28] They also provided some desirable strategies to access further materials with this type of motif. [29][30][31] This goal can be achieved by extending the degree of π conjugation within the materials, which affords smaller band gaps. Thus, there is substantial interest in the synthesis and photophysical properties of new families of planar structures with π-conjugated pure-blue light-emitting molecules.…”

An Effective Route to Dithieno[3,2-b:2′,3′-d]thiophene-Based Hexaheteroacenes

“…1,2 In this context, dithieno[3,2-b:2',3'-d]thiophene (DTT), due to rigid planar scaffold structure with high π-conjugation as well as ability to create effective intermolecular S…S interactions, has found a wide application in the design of p-type semiconductors, including (hetero)aryl-linked DTT molecules [3][4][5][6][7][8][9][10][11] as well as ringfused molecules with DTT core, [12][13][14][15][16][17][18] for organic field-effect transistors (OFET). In addition, DTT subunit has been also used for the construction of light-harvesting materials for organic photovoltaics, [19][20][21][22][23][24][25][26][27] electrochromic [28][29][30][31] and photochromic [32][33][34] materials. For instance, two selected semiconductor materials based on benzo-or indolo-fused DTT frameworks P-BTDT 12 and C6-DBTDT 17 or N,S-heteroheptacene 18 Figure 1, using the Fischer indolization reaction as the key transformation, 35 and shown its promising application as p-type organic semiconductor.…”

“…The DTT subunit has been also used in the construction of light-harvesting materials for organic photovoltaics, [9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27] as well as in electrochromic [28][29][30][31] and photochromic materials. [32][33][34] For instance, two examples of semiconductor materials based on benzo-fused DTT frameworks, P-BTDT 12 and C6-DBTDT, 17 together with an N,S-heteroheptacene with an indolo-fused DDT frame-work 18 used in the production of solution-processible OFETs, are shown in Figure 1. Furthermore, we recently described a synthesis of the N,S-heterohexacene 12H- [3,2-b]indole (BTTTI; also shown in Figure 1), by using a Fischer indolization reaction as a key transformation, 35 and we demonstrated its promising application as a ptype organic semiconductor.…”