Toward an Arsenic Analogue of Hittorf's Phosphorus:  Mixed Pnicogen Chains in Cu₂P_1.8As_1.2I₂

Abstract

The new compound Cu(2)P(1.8)As(1.2)I(2), with neutral, mixed pnicogen chains, has been synthesized from a stoichiometric combination of CuI, P, and As heated in vacuo at 550 degrees C. Cu(2)P(1.8)As(1.2)I(2) represents substitution of 40% of P in Cu(2)P(3)I(2) by As, with the As predominantly occupying "roof" positions in the tubular chains. The mixed pnicogen modification demonstrates increased stability (T(d) = 330 degrees C) relative to Cu(2)P(3)I(2) (T(d) = 290 degrees C) but a similar optical band gap (E(g) approximately 1.2 eV). Crystallographic data: Cu(2)P(1.8)As(1.2)I(2), monoclinic P2(1)/c, a = 15.477(3) A, b = 13.200(3) A, c = 15.421(3) A, beta = 115.406(4) degrees, Z = 16 (T = 293 K).

(CuBr)2P8Se3: preparation, structural, and vibrational spectroscopic characterization of an adduct of P8Se3 cages to Cu2Br2 rhombs

“…This gap was also derived from theoretical calculations for phosphorus rich molecules [16]. Transferring these findings to the phosphorus rich P 8 Se 3 molecule one should observe a similar separation of bending and stretching modes in (CuBr) 2 P 8 Se 3 and (CuI) 2 P 8 Se 3 .…”

“…Thus, a number of phosphorus polymers, chalcogen molecules and phosphorus chalcogenides could be obtained as their adducts to copper(I) halides. Recently, even an arsenic substituted phosphorus polymer embedded in CuI was reported [3]. In addition to their ion conducting properties, these compounds can be used as model compounds for the basic characterization of copper containing phosphorus chalcogenide glasses by solid state NMR spectroscopy [4].…”

Phosphides: Solid‐State Chemistry

“…260 The mixed pnictogen modifications demonstrates an increased stability relative to Cu 2 P 3 I 2 .…”

Structure–Property Correlations in Solid Solutions of (CuI)8P12−xAsx, 2.4≤x≤6.6

“…Synthesis and composition of mixed pnicogen compoundsprobing the limits of As incorporation: The ability to synthesize P/As mixed pnicogen compounds with As up to 40 % [10] led us to question just how much As can in fact be substituted for P in (CuI) 8 P 12 ; accordingly, syntheses of (CuI) 8 P 12Àx As x phases with As content up to 90 % were carried out using conventional high-temperature ampoule techniques. Stoichiometric amounts of CuI, red P, and elemental As were ground together, pressed into a pellet, placed in an alumina boat, and heated at 550 8C for two weeks in an evacuated fused silica jacket.…”

“…Although the logical end products (CuI) 8 As 12 and (CuI) 8 Sb 12 do not appear to be stable, we discovered that solid solutions of P/As chains could be prepared and a new compound, (CuI) 8 P 7.2 As 4.8 , in which 40 % of P is substituted by As, has been reported. [10] This compound is isostructural to its parent compound, (CuI) 8 P 12 , consisting of alternating Pn 8 cages and Pn 4 …”