This paper describes the p‐type semiconductor characteristics of 1‐arylmethyl‐substituted air‐tolerant 1,3‐diphosphacyclobutane‐2,4‐diyls, focusing preliminarily on their hole transfer parameters deduced from their crystal and density functional theory (DFT) structures. 1‐(2‐Anthrylmethy)‐3‐t‐butyl‐2,4‐bis(2,4,6‐tri‐t‐butylphenyl)‐1,3‐diphosphacyclobutane‐2,4‐diyl functions as a p‐type field‐effect transistor (FET) with semiconductor parameters comparable to its benzyl‐substituted derivative. Thienylmethyl groups induced the FET response, and thus we investigated the utility of the 2‐thieno[3,2‐b]thiophenemethyl group. Critical parameters, including reorganization energies (λ), hole couplings (V), and hole hopping rates (W) were estimated based on experimental and DFT data. The benzyl and 2‐anthrylmethy groups constructed hole transfer pathways comparable to that of acenes, whereas the 2‐thieno[3,2‐b]thiophenemethyl substituent resulted in the assembly of a unique three‐dimensional network. The findings described in this study may lead to the fabrication of superior FET devices based on the chemistry of 1,3‐diphosphacyclobutane‐2,4‐diyl.

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A heterobimetallic trinuclear complex of Ru and Pt in a linear alignment, {Cp*Ru­(H)2}2(Pt)­(μ-PtBu2)2(μ-H)2 (2; Cp* = η5-C5Me5), was synthesized via P–C bond scission upon the photolysis of Cp*Ru­(μ-H)4RuCp* (1) in the presence of Pt­(PtBu3)2. Complex 2 was alternatively synthesized by the reaction of 1 with Pt­(PtBu2H)3, together with the formation of a triangular Ru2Pt complex, (Cp*Ru)2{Pt­(PtBu2H)}­(μ-PtBu2)­(μ-H)3(H)2 (4). X-ray diffraction experiments showed that the structure of 2 could be regarded as a dimer of [Cp*RuH3(PtBu2)]− fragments linked by a Pt2+ ion. In contrast to the relevant monometallic trihydrido complex of ruthenium, Cp*RuH3(PtR3), terminal hydrides of 2 were readily substituted by CO and ethylene, leading to the formation of {Cp*Ru­(L)}2(Pt)­(μ-PtBu2)2(μ-H)2 (5; L = CO, 6; L = C2H4). Such high reactivity could be attributed to the facile formation of a coordinatively unsaturated intermediate owing to stabilization by bulky μ-PtBu2 moieties as well as electronic influence of the central Pt atom. In fact, terminal hydrides of 2 were readily removed upon evacuation, leading to the formation of tetra- and dihydrido complexes (Cp*Ru)­{Cp*Ru­(H)2}­Pt­(μ-PtBu2)2(μ-H)2 (3) and (Cp*Ru)2­Pt­(μ-PtBu2)2(μ-H)2 (8), consecutively. Upon hydrogenation, 3 and 8 were smoothly transformed into 2. In contrast with the reactions of 2 with 2e donors, substitution at the Pt atom occurred in reactions with Ph2SiH2 and Et2SiH2, resulting in μ-silylene and μ-silyl complexes {Cp*Ru­(H)}­{Cp*Ru­(PtBu2H)}­Pt­(μ-PtBu2)­(μ-SiPh2)­(μ-H)2 (9) and {Cp*Ru­(H)2}­{Cp*Ru­(PtBu2H)}­Pt­(μ-PtBu2)­(μ-η2-SiEt2)­(μ-H)2 (10), respectively. In these reactions, the μ-phosphido ligand bridging the Ru and Pt atoms was transformed into a terminal phosphine ligand at the peripheral Ru atom, alongside the formation of μ-silylene and μ-silyl ligands via reductive P–H bond formation.