The title heterobridge system exhibits the coexistence of AF ordering, SCM-derived multi-relaxation dynamics, field-induced metamagnetism and field-induced spin-glass-like dynamics.

Various zwitterionic carboxylate ligands form MnII coordination polymers with carboxylate and pseudo‐halide bridges mixed in different ways. With mono‐zwitterions, [Mn(N3)2(L1)(H2O)]n and [Mn(N3)2(L2)]n contains 1D chains with (μ‐1,1‐N3)(μ‐1,3‐OCO) and (μ‐1,1‐N3)2(μ‐1,3‐OCO) bridges, respectively. With di‐zwitterions, [Mn(N3)(L3)]n(ClO4)n forms a 2D network based on chains with (μ‐1,1‐N3)(μ‐1,3‐OCO)2 bridges, whereas [Mn2(X)4(L4)]n·2nH2O (X = N3 or NCO) are interpenetrating 3D networks based on chains with (μ‐1,1‐X)2(μ‐1,3‐OCO) bridges. With a tri‐zwitterion, [Mn7(N3)14(OH)2(L5)(H2O)6]n·4nH2O is a 2D network based on a novel chain in which μ‐1,1‐N3‐ and μ‐1,3‐OCO‐bridged trinuclear motifs and μ3‐OH‐ and μ‐1,1‐N3‐bridged tetranuclear motifs are linked by μ‐1,3‐N3 and μ3‐1,1,3‐N3. All compounds exhibit antiferromagnetic interactions, the magnitude of which depends upon the nature and mixing mode of the bridges, and follow the trend (μ‐N3)(μ‐OCO) < (μ‐N3)(μ‐OCO)2 < (μ‐N3)2(μ‐OCO) < (μ‐NCO)2(μ‐OCO).

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