Exploration of 1-Arylmethyl-1,3-diphosphacyclobutane-2,4-diyls as Hole Transfer Materials

Abstract

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.

Observation of a Metastable P‐Heterocyclic Radical by Muonium Addition to a 1,3‐Diphosphacyclobutane‐2,4‐diyl

“…In this study, we employed the air‐stable 1,3‐diphosphacyclobutane‐2,4‐diyl 1 (Figure ) and 1,3,5‐tri‐ t ‐butylbenzene (Mes*H) for μSR spectroscopy. The data obtained from 1 , bearing the Mes* substituents and benzyl group, were expected to be easily analyzed by utilizing the information about Mes*H. A brief description of the μSR techniques used in this study is given in the Supporting Information and in the literature .…”

Study of the Air‐Tolerant 1,3‐Diphosphacyclobutane‐2,4‐diyl through the Direct Arylation

“…Such electron‐donating character of the air‐tolerant P‐heterocyclic singlet biradicals was quite attractive to develop novel electro‐functional organic materials. We recently reported the p‐type semiconductor behavior of highly air‐stable 2,4‐bis(2,4,6‐tri‐ t ‐butylphenyl)‐1‐ t ‐butyl‐3‐arylmethyl‐1,3‐diphosphacyclobutane‐2,4‐diyls . Also, the directly arylated 1,3‐diphosphacyclobutane‐2,4‐diyls have been investigated from the views of semiconductor characters.…”

“…Figure shows the effective hole‐transfer pathways in the single crystal of 5 h , and Table summarizes the estimated hole coupling matrix element ( V ), hole hopping rate ( W ), and mass center distances ( r ). The L 2 and L 3 (= T 3 ) dimers show the smaller hole hopping rates, which would relate to the inferior semiconductor character to that of 2,4‐bis(2,4,6‐tri‐ t ‐butylphenyl)‐1‐ t ‐butyl‐3‐arylmethyl‐1,3‐diphosphacyclobutane‐2,4‐diyl …”

Observation of a Metastable P‐Heterocyclic Radical by Muonium Addition to a 1,3‐Diphosphacyclobutane‐2,4‐diyl

“…In this study,w ee mployed the air-stable 1,3-diphosphacyclobutane-2,4-diyl 1 (Figure 1) [8,9,22] and 1,3,5-tri-t-butylbenzene (Mes*H) for mSR spectroscopy.T he data obtained from 1,bearing the Mes* substituents and benzyl group,were expected to be easily analyzed by utilizing the information about Mes*H. Abrief description of the mSR techniques used in this study is given in the Supporting Information and in the literature. [16][17][18][19][20] Themuon beamline at the TRIUMF cyclotron (M15) was used, and the Helios spectrometer was equipped with the superconducting solenoid magnet.…”

“…[5,6] Most air-tolerant 1t-butyl-2,4-bis(2,4,6-tri-t-butylphenyl)-1,3-diphosphacyclobu-tane-2,4-diyls,i ncluding 1,w ork as electron donors, [7] and several derivatives are useful for fabricating low-voltage pchannel transistors. [8][9][10] Also,t he presence of tervalent phosphorus atoms enables access to particular phosphorus heterocycles by valence expansion, and processes for formal capture of dihydrogen [11] and sensing of hydrogen fluoride [10,12] have been developed.…”