Suit[3]ane

Abstract

Suitanes are a class of mechanically interlocked molecules (MIMs) that consist of two components: a body with limbs protruding outward and a suit that fits appropriately around it, so that there is no easy way for the suit to be removed from the body. Herein, we report the synthesis and characterization of a suit[3]ane, which contains a benzotrithiophene derivative (THBTT) with three protruding hexyl chains as the body and a 3-fold symmetric, extended pyridinium-based cage, namely, HexaCage 6+ , as the suit. Central to its realization is effective templation, provided by THBTT during cage formation, an observation that has been supported by the strong binding constant between benzotrithiophene (BTT) and the empty cage. The solidstate structure of the suit[3]ane reveals that the body is confined within the suit's cavity with its alkyl chains protruding outward through the orifices in the cage. Notably, such a seemingly unstable molecule, having three flexible alkyl chains as its only protruding limbs, does not dissociate after prolonged heating in CD 3 CN at 100 °C under pressure for 7 days. No evidence for guest exchange with the host was observed at this temperature in a 2:1 mixture of THBTT and HexaCage 6+ in CD 3 CN. The results indicate that flexible protruding limbs are sufficient for a suit[3]ane to remain mechanically stable even at high temperatures in solution.

Organic Thin‐film Solar Cells Using Benzotrithiophene Derivatives Bearing Acceptor Units as Non‐Fullerene Acceptors

“…Melting point was measured by using a Yanaco MPÀ J3. 1 H and 13 C NMR spectra were measured by using a Varian MERCURY 300 ( 1 H, 300 MHz; 13 C, 75 MHz) and a JEOL JNM-ECS 400 ( 1 H, 400 MHz; 13 C, 100 MHz). Unless otherwise noted, CDCl 3 was used as NMR solvent.…”

“…In particular, a benzotrithiophene unit with a star-shaped πconjugated plane including three thiophene units is one of the most attractive π-conjugated molecular units because of its ability to form π-conjugated column structures with high carrier mobilities suitable for organic optoelectronic materials. Recently, organic π-conjugated molecules, including the benzotrithiophene unit, are attracting interest, and a variety of applications related to supramolecules, [1] metal-organic frameworks (MOFs), [2] covalent organic frameworks (COFs), [3][4] magneto-optical materials, [5] non-fullerene acceptors for organic solar cells, [6][7][8][9][10] organic polymer solar cells, [11,12] a hole transporting layer of perovskite solar cells, [13][14][15] and field-effect transistors (FETs) [16] have been reported.…”

“…was purified by flash silica gel column chromatography (hexane/ EtOAc = 5 : 1) to give the title compound 6 (5.66 g, 20.33 mmol, 57 % yield, orange viscous liquid) 1. H NMR (400 MHz, CDCl 3 ) δ 7.13 (d, J = 5.2 Hz, 1H), 6.84 (d, J = 5.2 Hz, 1H), 2.66 (t, J = 8.0 Hz, 2H), 2.00-2.07 (br s, 1H), 1.62 (s, 6H), 1.60 (quintet, J = 8.0 Hz, 2H), 1.20-1.36 (br m, 10H), 0.88 (t, J = 7.0 Hz, 3H) ppm;13 C NMR (100 MHz, CDCl 3 ) δ 147.9, 128.1, 125.7, 117.4, 99.5, 75.2, 65.8, 31.9, 31.4, 30.1, 29.4, 29.3, 22.7, 14.1 ppm.…”

“…The solution was filtered and concentrated, followed by reprecipitation with EtOAc/MeOH to give the title compound 11 (2.08 g, 2.51 mmol, 81 % yield, brown solid, m.p. = 76.7°C-81.6°C) 1. H NMR (400 MHz, CDCl 3 ) δ 7.57 (s, 3H), 7.28 (d, J = 5.6 Hz, 3H), 7.01 (d, J = 5.6 Hz, 3H), 2.90 (t, J = 7.6 Hz, 6H), 1.71 (quintet, J = 7.6 Hz, 6H), 1.05-1.48 (br m, 30H), 0.84 (t, J = 7.0 Hz, 9H) ppm;13 C NMR (100 MHz, CDCl 3 ) δ 140.9, 135.8, 131.4, 131.2, 130.23, 130.17, 124.8, 120.4, 31.9, 30.7, 29.5, 29.4, 29.3, 22.7, 14.1 ppm.…”

“…Cl 2 ), followed by the reprecipitation with Et 2 O/ hexane to give the title compound 17 (1.12 g, 4.04 mmol, 76 % yield, yellow-white solid (crystal), m.p. = 75.0°C-76.2°C) 1. H NMR (400 MHz, CDCl 3 ) δ 4.08 (t, J = 7.6 Hz, 2H), 4.01 (s, 2H), 1.69 (quintet, J = 7.6 Hz, 2H), 1.20-1.44 (br m, 10H), 0.88 (t, J = 6.8 Hz, 3H) ppm; 13 C NMR (100 MHz, CDCl 3 ) δ 171.6, 171.5, 112.8, 111.7, 56.5, 45.3, 32.3, 31.6, 29.0, 28.5, 25.8, 22.5, 14.0 ppm.…”