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New Pb(II)‐Ammine complexes as intermediates from the interaction of CH 3 NH 2 with PbX 2 and CH 3 NH 3 PbX 3 (X=Cl, Br)
Author(s) -
Krummer Michael,
Daub Michael,
Hillebrecht Harald
Publication year - 2022
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.202100176
Subject(s) - octahedron , chemistry , crystallography , halide , chloride , stereochemistry , crystal structure , inorganic chemistry , organic chemistry
In continuation of our investigations of the “molten salt approach” for MAPbI 3 , we now report on the interaction of gaseous CH 3 NH 2 with Pb X 2 ( X =Cl, Br) and MAPb X 3 ( X =Cl, Br). We have characterized cubic [Pb(CH 3 NH 2 ) 6 ]Br 2 with a close similarity to the K 2 PtCl 6 type and partially disordered octahedra [Pb(CH 3 NH 2 ) 6 ] 2+ . Release of CH 3 NH 2 yields Pb(CH 3 NH 2 ) 3 Br 2 . Here Pb 2+ is octahedrally coordinated by 3 CH 3 NH 2 ligands and 3 Br − as a fac ‐isomer. Charge neutrality is achieved by one terminal and two bridging Br − forming edge‐sharing dimers. For the chloride there is only a partial exchange of the halide ligands. Pb(CH 3 NH 2 ) 2 Cl 2 , with a novel cubic structure, shows two different octahedra: PbCl 6 and Pb(CH 3 NH 2 ) 3 Cl 3 . Pb(CH 3 NH 2 ) 3 Cl 2 is closely related to Pb(CH 3 NH 2 ) 3 Br 2 , i. e. Pb(CH 3 NH 2 ) 3 Cl 3 octahedra in fac ‐geometry with one terminal and two bridging Cl − , but herez the polyhedra form a linear chain. In all representatives with mixed ligands the interaction with X − is significantly weaker than with CH 3 NH 2 . H‐bridges N−H⋅⋅⋅X contribute to the interaction between the Pb(CH 3 NH 2 ) 3 X 3 units. All compounds decompose in air to Pb(OH) X and MAPb X 3 ( X =Cl, Br).