Hämmer Matthias, Pielnhofer Florian, Janka Oliver, Takahashi Hirotaka, Gross Peter, Pöttgen Rainer, Höppe Henning A
Institut für Physik, Universität Augsburg, Universitätsstraße 1, 86159 Augsburg, Germany.
Institut für Anorganische Chemie, Universität Regensburg, Universitätstraße 31, 93053 Regensburg, Germany.
Dalton Trans. 2022 Feb 22;51(8):3104-3115. doi: 10.1039/d1dt04090a.
Two polymorphs of the borosulfate Cu[B(SO)] can be selectively prepared by solvothermal syntheses. The crystal structures of inosilicate-analogous α-Cu[B(SO)] (1̄, no. 2, = 5.2636(2), = 7.1449(2), = 7.9352(2) Å, = 73.698(2)°, = 70.737(2)°, = 86.677(2)°, 65 parameters, = 0.0052) and the new phyllosilicate-analogous polymorph β-Cu[B(SO)] (2/, no. 14, = 7.712(3), = 8.149(3), = 9.092(3) Å, = 111.22(1)°, 3829 independent reflections, 106 parameters, = 0.054) are discussed. Further, the optical, magnetic and thermal properties of both polymorphs are investigated with focus on the role of the Cu cation and its Jahn-Teller effect. The findings are confirmed by DFT calculations yielding insights in the stability of the synthesised polymorphs as well as a predicted γ-modification. Additionally, the crystal structures of two polymorphs of copper hydrogensulfate Cu(HSO)-I (2/, no. 14, = 4.7530(2), = 8.5325(4), = 7.3719(3) Å, = 100.063(1)°, 1063 independent reflections, 55 parameters, = 0.052) and Cu(HSO)-II (1̄, no. 2, = 4.79.88(8), = 7.857(1), = 8.057(1) Å, = 77.86(1)°, = 87.02(1)°, = 89.82(1)°, 1044 independent reflections, 109 parameters, = 0.132) as well as that of Cu[SO] (2/, no. 15, = 6.6341(4), = 8.7302(5), = 9.0555(8) Å, = 104.763(3)°, 1117 independent reflections, 48 parameters, = 0.049) are presented and the cyclosilicate-analogous borosulfate Cu[B(SO)(HSO)] is fully characterised with respect to its optical and thermal properties.
通过溶剂热合成法可以选择性地制备硼硫酸盐Cu[B(SO)]的两种多晶型物。讨论了类链硅酸盐的α-Cu[B(SO)]（1̄，编号2，= 5.2636(2)，= 7.1449(2)，= 7.9352(2) Å，= 73.698(2)°，= 70.737(2)°，= 86.677(2)°，65个参数，= 0.0052）和新的类层状硅酸盐多晶型物β-Cu[B(SO)]（2/，编号14，= 7.712(3)，= 8.149(3)，= 9.092(3) Å，= 111.22(1)°，3829个独立反射，106个参数，= 0.054）的晶体结构。此外，研究了两种多晶型物的光学、磁性和热性质，重点关注Cu阳离子的作用及其 Jahn-Teller 效应。通过密度泛函理论（DFT）计算证实了这些发现，该计算揭示了合成多晶型物的稳定性以及预测的γ-变体。此外，还给出了硫酸氢铜Cu(HSO)-I（2/，编号14，= 4.7530(2)，= 8.5325(4)，= 7.3719(3) Å，= 100.063(1)°，1063个独立反射，55个参数，= 0.052）和Cu(HSO)-II（1̄，编号2，= 4.79.88(8)，= 7.857(1)，= 8.057(1) Å，= 77.86(1)°，= 87.02(1)°，= 89.82(1)°，1044个独立反射，109个参数，= 0.132）以及Cu[SO]（2/，编号15，= 6.6341(4)，= 8.7302(5)，= 9.0555(8) Å，= 104.763(3)°，1117个独立反射，48个参数，= 0.049）的两种多晶型物的晶体结构，并对类环状硅酸盐硼硫酸盐Cu[B(SO)(HSO)]的光学和热性质进行了全面表征。
