New Solids in As-O-Mo, As(P)-O-Mo(W) and As(P)-O-Nb(W) Systems That Exhibit Nonlinear Optical Properties

Gerasimchuk, Nikolay; Kivijarvi, Lauri; Noll, Bruce; Goudjil, Meriem; Khanra, Soma; Ping, Yu; Pearson, Miles; Röminger, Frank

doi:10.3390/molecules26051494

Title: New Solids in As-O-Mo, As(P)-O-Mo(W) and As(P)-O-Nb(W) Systems That Exhibit Nonlinear Optical Properties

Journal Article · Tue Mar 09 00:00:00 EST 2021 · Molecules

DOI:https://doi.org/10.3390/molecules26051494· OSTI ID:1817015

Gerasimchuk, Nikolay ^[1]; Kivijarvi, Lauri ^[1]; Noll, Bruce ^[2]; Goudjil, Meriem ^[3]; Khanra, Soma ^[4];

^[4]; Pearson, Miles ^[1]; Röminger, Frank ^[5]

Missouri State University, Springfield, MO (United States). Dept. of Chemistry
Bruker AXS, Inc., Madison, WI (United States)
Université des Sciences et de la Technologie Houari Boumediène, Alger (Algeria). Faculte de Chimie. Laboratorie des Sciences des Materiaux
Univ. of Missouri, Columbia, MO (United States). Dept. of Physics and Astronomy
Heidelberg Univ. (Germany). Organisch-Chemisches Institut der Universität Heidelberg Lehrstuhl für Organische Chemie III

Interactions between well-mixed fine powders of As₂O₃, P₂O₅, MoO₃, WO₃ and Nb₂O₅ at different stoichiometry in quartz ampoules under vacuum at ~1000 °C in the presence of metallic molybdenum (or niobium), over several weeks, led to shiny dichroic crystalline materials being formed in cooler parts of the reaction vessel. An addition of small quantities of metals-Mo or Nb-was made with the aim of partially reducing their highly oxidized Mo(VI), W(VI) or Nb(V) species to corresponding Mo(V), W(V) and Nb(IV) centers, in order to form mixed valence solids. Sublimed crystals of four new compounds were investigated using a variety of techniques, with prime emphasis on the X-ray analysis, followed by spectroscopy (diffusion reflectance, IR, Raman and EPR), second harmonic generation (SHG), thermal analysis under N₂ and air atmosphere, and single crystals electrical conductivity studies. The results evidenced the formation of new complex solids of previously unknown compositions and structures. Three out of four compounds crystallized in non-centrosymmetric space groups and represent layered 2D polymeric puckered structures that being stacked on each other form 3D lattices. All new solids exhibit strong second-harmonic-generation (SHG effect; based on YAG 1064 nm tests with detection of 532 nm photons), and a rare photosalient effect when crystals physically move in the laser beam. Single crystals’ electrical conductivity of the four new synthesized compounds was measured, and the results showed their semiconductor behavior. Values of band gaps of these new solids were determined using diffusion reflectance spectroscopy in the visible region. Aspects of new solids’ practical usefulness are discussed.

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Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1817015

Journal Information:: Molecules, Vol. 26, Issue 5; ISSN 1420-3049

Publisher:: MDPICopyright Statement

Country of Publication:: United States

Language:: English

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Title: New Solids in As-O-Mo, As(P)-O-Mo(W) and As(P)-O-Nb(W) Systems That Exhibit Nonlinear Optical Properties

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