A series of complexes of the type Tp'Rh(PR(3))(Ar(F))H, where PR(3) = PMe(3) (3) and PMe(2)Ph (9), Ar(F) = C(6)F(5) (a), 2,3,4,5-C(6)F(4)H (b), 2,3,5,6-C(6)F(4)H (c), 2,4,6-C(6)F(3)H(2) (d), 2,3-C(6)F(2)H(3) (e), 2,5-C(6)F(2)H(3) (g), and 2-C(6)FH(4) (h) and Tp' = tris(3,5-dimethylpyrazolyl)borate, has been synthesized as stable crystalline compounds by the reactions of the [Tp'Rh(PR(3))] fragment with the corresponding fluorinated aromatic hydrocarbons, and their structures were characterized by NMR spectroscopy and elemental analysis together with X-ray crystallography. The kinetics of the reductive eliminations of fluoroarenes from complexes 3a-h in benzene-d(6) solutions at 140 °C were investigated, but were complicated by the formation of the rhodium(I) bisphosphine complex, Tp'Rh(PMe(3))(2) (4). On the other hand, thermal reactions of (9) in THF-d(8) solutions at 120 °C resulted in the formation of an intramolecular C-H bond activated complex of the phenyl group on the phosphorus atom, Tp'Rh(κ(2)-C(6)H(4)-2-PMe(2))H (7), which prevents the formation of the corresponding bisphosphine complex. The experimentally determined rates of the reductive eliminations of fluoroarenes from the complexes 9a-h and their kinetic selectivities for formation in competition with the metallacycle have been used to determine relative Rh-CAr(F) bond energies. The Rh-CAr(F) bond energy is found to be dependent on the number of ortho fluorines. A plot of Rh-CAr(F) vs. C-H bond strengths resulted in a line with a slope R(M-C/C-H) of 2.15 that closely matches the DFT calculated value (slope = 2.05).

Mixed composition metal–halide perovskites were developed to improve the performance of perovskite solar cell devices incorporating tin(iv) oxide substrates for electron transport layers by optimizing the I/Br halide ion ratio.

The [Tp 0 Rh(PR 3 )] fragments, where Tp 0 = tris(3,5-dimethylpyrazolyl)borate, R 3 = Me 3 (a) or PhMe 2 (b), were shown to be applicable for the activation of the C-H and C-CN bonds of acetonitrile. The photoirradiation of Tp 0 Rh(PR 3 )H 2 (1a,b) in acetonitrile at room temperature afforded the complexes Tp 0 Rh(PR 3 )(CH 2 CN)H (3a,b), by the selective oxidative addition of the primary C-H bond of acetonitrile to the [Tp 0 Rh(PR 3 )] fragment generated by the dehydrogenation of 1. The thermal reactions of Tp 0 Rh(PMe 3 )(Ph)H (2a) or Tp 0 Rh(κ 2 -C 6 H 4 -2-PMe 2 )H (2b) in acetonitrile at 80°C also resulted in the formation of 3a and 3b, respectively, by the oxidative addition of the C-H bond to the [Tp 0 Rh(PR 3 )] fragment, generated by the reductive elimination of benzene (from 2a) or intramolecular reductive elimination of the PPhMe 2 ligand (from 2b). Heating the isolated C-H bond activated complexes 3a,b in acetonitrile at higher temperature (100°C) for longer times (≈5 days) resulted in the formation of the corresponding C-CN bond activated complexes, Tp 0 Rh(PR 3 )(CH 3 )(CN) (4a,b), respectively. The molecular structures of the C-H activated product 3a,b (kinetic product) and C-CN activated product 4a,b (thermodynamic product) were fully characterized by NMR spectroscopy, elemental analysis, and X-ray crystallographic analysis. Furthermore, the secondary C-H bond activated product of succinonitrile, Tp 0 Rh(PMe 3 )[CH(CN)CH 2 CN]H (5), was isolated by the thermal reaction of 2a with succinonitrile (20 equiv) at 100°C, and the molecular structure was characterized by NMR spectroscopy and X-ray crystallographic analysis. The cleavage of CH 3 CN was also investigated using DFT models to compare thermodynamics and identify transition-state geometries.

A series of cost-effective hole-transporting materials (TOP-HTMs) for perovskite solar cells (PSCs) was designed and synthesized. The molecules, composed of multiple 4,4′-dimethoxytriphenylamines linked to a benzene core via trans-vinylene units, can be manufactured from inexpensive materials through a simple synthetic route. The photophysical, electrochemical, and thermal properties, as well as hole mobilities, were strongly influenced by the position and number of vinyl triarylamine substituents on the core benzene ring. CH3NH3PbI3-based solar cells using the X-shaped TOP-HTM 3 with additives gave a high power conversion efficiency of 17.5% (forward scan)/18.6% (reverse scan). Crucially, TOP-HTMs gave high working device efficiency without the need for conduction-enhancing additives. The power conversion efficiency for the device with additive-free TOP-HTM 3 was 16.0% (forward scan)/16.6% (reverse scan). Device stability is also enhanced and is superior to the reference HTM, 2,2′,7,7′-tetrakis­(N,N-di-p-methoxyphenylamine)-9,9′-spirobifluorene (Spiro-OMeTAD).

In this paper, we report the synthesis and the structural characterization of stable examples of silanedithiol [Tbt(Mes)Si(SH)2 (1)], hydroxysilanethiol [Tbt(Mes)Si(OH)(SH) (3)], and hydroxysilaneselenol [Tbt(Mes)Si(OH)(SeH) (7)], which are kinetically stabilized by an effective combination of steric protection groups, Tbt (2,4,6‐tris[bis(trimethylsilyl)methyl]phenyl) and Mes (2,4,6‐trimethylphenyl). Silanedichalcogenols 1, 3, and 7 are suggested to exist as a monomer without any intermolecular contact such as hydrogen bonds both in the solid state and in solution as judged by X‐ray structural analysis and IR spectroscopy. Treatment of 1 with 2 equiv. of butyllithium resulted in the quantitative formation of the corresponding dilithium silanedithiolate, Tbt(Mes)Si(SLi)2 (8), the generation of which was confirmed by a trapping experiment using MeI. Furthermore, the addition of cis‐[MCl2(PPh3)2] (M = Pd, Pt) to a THF solution of 8 afforded the corresponding silanedithiolato complexes, [Tbt(Mes)Si(μ‐S)2M(PPh3)2] (9a: M = Pd; 9b: M = Pt), respectively. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)