Novel isomorphism of two hexagonal non-centrosymmetric hybrid crystals of M(en)₃Ag₂I₄ (M = transition metal Mn²⁺ or main-group metal Mg²⁺; en = ethylenediamine)

Abstract

For the first time, a main-group metal complex is used as a template for the formation of hybrid crystal structures and isomorphic hybrid crystals are obtained using transition and main-group metal complexes.

Comprehensively Understanding Isomorphism and Photoluminescent Nature of Two-Dimensional Coordination Polymers of Cd(II) and Mn(II) with 1,1′-Ethynebenzene-3,3′,5,5′-tetracarboxylic Ligand

“…40 Moreover, all metal centers in the M(en) 3 2+ in this family of M(en) 3 Ag 2 I 4 (M 2+ = Mg 2+ , Mn 2+ , Ni 2+ , Zn 2+ and Cd 2+ ) show approximately spherical electron cloud distribution, however, the metal ion with non-spherical electron cloud distribution, for example, M 2+ = Cu 2+ or Co 2+ ion, directs to give differently structural inorganic silver-iodide framework or failed to achieve the crystals even if the self-assembly undergoes under the same condition. 40,46 These observations suggest that the electron configuration of the metal centers in the coordination compounds, in some cases, is also one of the critical factors to affect the formation isomorphs. In the isomorphic [M 3 (HEBTC) 2 (DMSO) 6 ] (M = Cd (1) and Mn 8 ), the Mn 2+ and Cd 2+ centers have distorted octahedral coordination environment formation by the oxygen atoms from carboxyl groups or DMSO molecules.…”

“…2+ (where M 2+ = Mg 2+ , Mn 2+ , Ni 2+ , Zn 2+ and Cd 2+ ) with symmetry of D 3 point group, plays an important role in the process of directing the formation of three-dimensional hexagonal non-centrosymmetric framework of {Ag 2 I 4 2− } ∞ . 40 Moreover, all metal centers in the M(en) 3 2+ in this family of M(en) 3 Ag 2 I 4 (M 2+ = Mg 2+ , Mn 2+ , Ni 2+ , Zn 2+ and Cd 2+ ) show approximately spherical electron cloud distribution, however, the metal ion with non-spherical electron cloud distribution, for example, M 2+ = Cu 2+ or Co 2+ ion, directs to give differently structural inorganic silver-iodide framework or failed to achieve the crystals even if the self-assembly undergoes under the same condition. 40,46 These observations suggest that the electron configuration of the metal centers in the coordination compounds, in some cases, is also one of the critical factors to affect the formation isomorphs.…”

“…The isomorphism is an appealing phenomenon and commonly observed in the rare-earth metal MOFs/CPs, and this is because that the lanthanide ions have fairly close ionic radii, the same outermost electron configuration and positive charge, etc. , The isomorphism phenomenon has been also found in the transition-metal MOFs/CPs, although it is not as common as in the rare-earth metal MOFs/CPs. − Most recently, Ren et al investigated the crystal structures of a series of three-dimensional open-framework hybrid crystals of M­(en) 3 Ag 2 I 4 (M 2+ = Mg 2+ , Mn 2+ , Ni 2+ , Zn 2+ , and Cd 2+ ; en = ethylenediamine), , and discovered that all members in this family are isomorphic and crystallize in the hexagonal non-centrosymmetric space group P 6 3 22 with fairly analogous cell parameters at room temperature, and the metal coordination cation, M­(en) 3 2+ (where M 2+ = Mg 2+ , Mn 2+ , Ni 2+ , Zn 2+ and Cd 2+ ) with symmetry of D 3 point group, plays an important role in the process of directing the formation of three-dimensional hexagonal non-centrosymmetric framework of {Ag 2 I 4 2– } ∞ . Moreover, all metal centers in the M­(en) 3 2+ in this family of M­(en) 3 Ag 2 I 4 (M 2+ = Mg 2+ , Mn 2+ , Ni 2+ , Zn 2+ and Cd 2+ ) show approximately spherical electron cloud distribution, however, the metal ion with non-spherical electron cloud distribution, for example, M 2+ = Cu 2+ or Co 2+ ion, directs to give differently structural inorganic silver-iodide framework or failed to achieve the crystals even if the self-assembly undergoes under the same condition. , These observations suggest that the electron configuration of the metal centers in the coordination compounds, in some cases, is also one of the critical factors to affect the formation isomorphs. In the isomorphic [M 3 (HEBTC) 2 (DMSO) 6 ] (M = Cd ( 1 ) and Mn 8 ), the Mn 2+ and Cd 2+ centers have distorted octahedral coordination environment formation by the oxygen atoms from carboxyl groups or DMSO molecules.…”

“…38,39 The isomorphism phenomenon has been also found in the transition-metal MOFs/CPs, although it is not as common as in the rare-earth metal MOFs/CPs. 40−44 Most recently, Ren et al investigated the crystal structures of a series of threedimensional open-framework hybrid crystals of M(en) 3 Ag 2 I 4 (M 2+ = Mg 2+ , Mn 2+ , Ni 2+ , Zn 2+ , and Cd 2+ ; en = ethylenediamine), 40,45 and discovered that all members in this family are isomorphic and crystallize in the hexagonal non-centrosymmetric space group P6 3 22 with fairly analogous cell parameters at room temperature, and the metal coordination cation, M(en) 3…”

Solvated Lanthanide Cationic Template Strategy for Constructing Iodoargentates with Photoluminescence and White Light Emission

“…18−20 For instance, two iodoargentates, M(en) 3 Ag 2 I 4 (M = Mn 2+ and Mg 2+ ; en = ethylenediamine), were prepared by Ren's group, in which the structures could be subtly modulated by metal coordination cations. 21 Generally speaking, the effectiveness of these kinds of templates to fabricate iodometallates has been confirmed in recent publications. Meanwhile, the inorganic templates are relatively less compared with the flourishing development of the others, greatly limiting the assembly of corresponding products.…”