Two series of 2,5‐di(butoxy)phenyleneethynylenes, one halogenated (nPEC4‐X; n=2, 3, or 4) and the other boron‐dipyrromethene (BODIPY) terminated (nPEC4‐By; n=3, 4, or 5; By=BODIPY), were synthesized monodirectionally by the step‐by‐step approach and the molecular structure was corroborated by NMR spectroscopy (1H, 13C‐DEPTQ‐135, COSY, HSQC, HMBC, 11B, 19F) and MALDI‐TOF mass spectrometry. The multiplicity and J‐coupling constants of 1H, 11B, and 19F/11B NMR signals revealed, in the nPEC4‐By series, that the phenyl in the meso position of BODIPY becomes electronically part of the conjugation of the phenyleneethynylene chain, whereas BODIPY is electronically isolated. The photophysical, electrochemical, and theoretical studies confirm this finding because the properties of nPEC4‐By are comparable to those of the nPEC4‐X oligomers and BODIPY, indicating negligible electron communication between BODIPY and the nPEC4 moieties. Nevertheless, energy transfer (ET) from nPEC4 to BODIPY was rationalized by spectroscopy and theoretical calculations. Its yield decreases with the nPEC4 conjugation length, according to the increase in distance between the two chromophores, resulting in dual emission for the longest oligomer in which ET is quenched.

The fabrication, molecular structure, and spectroscopy of a stable cholesteric liquid crystal platinum acetylide glass obtained from trans-Pt(PEt 3) 2 (CC− C 6 H 5 −CN)(CC−C 6 H 5 −COO−Cholesterol), are described and designated as PE1-CN-Chol. Polarized optical microscopy, differential scanning calorimetry, and wide-angle X-ray scattering experiments show room temperature glassy/ crystalline texture with crystal formation upon heating to 165 °C. Further heating results in conversion to cholesteric phase. Cooling to room temperature leads to the formation of a cholesteric liquid crystal glass. Scanning tunneling microscopy of a PE1-CN-Chol monolayer reveals self-assembly at the solid−liquid interface with an array of two molecules arranged in pairs, oriented head-to-head through the CN groups, giving rise to a lamella arrangement. The lamella structure obtained from molecular dynamics calculations shows a clear phase separation between the conjugated platinum acetylide and the hydrophobic cholesterol moiety with the lamellae separation distance being 4.0 nm. Ultrafast transient absorption and flash photolysis spectra of the glass show intersystem crossing to the triplet state occurring within 100 ps following excitation. The triplet decay time of the film compared to aerated and deoxygenated solutions is consistent with oxygen quenching at the film surface but not within the film. The high chromophore concentration, high glass thermal stability, and long triplet lifetime in air show that these materials have potential as nonlinear absorbing materials.

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