The crystal of a valence tautomeric cobalt complex, [Co(dbbq) 2 (bpym)](1) (dbbq = 3,6-di-tert-butyl-1,2-benzoquinone and bpym = 2,2Ј-bipyrimidine), have been obtained by reaction between Co 2 (CO) 8 and dbbq in the presence of the ligand bpym in a mixed solvent under an N 2 atmosphere. The magnetic behavior of complex 1 clearly indicates that electron transfer from the catecholate ligand to the Co III cen-

A series of lanthanide(III)-Ag(I) 4d-4f heterometallic coordination polymers (HCPs) with pcu topology, {[Ln III -Ag I (Hbidc)(bidc)(ox) 0.5 (H 2 O)] 3 H 2 O} n (Ln = Sm 1, Eu 2, Gd 3, Tb 4, Dy 5, Ho 6, Er 7, H 2 bidc =1H-benzimidazole-5,6dicarboxylic acid, ox=oxalate), have been synthesized through self-assembly reactions. All seven complexes are isostructural and have three-dimensional 2-fold interpenetrated structures, with both the organic ligand and oxalate groups acting as bridges. These new complexes crystallize with the same unique six-connected three-nodal net described by (10 8 3 12 3 16 4 3 18 2 ) (10) 6 topology. The ferromagnetic properties of complex 3 were investigated. Moreover, complexes 1, 2, 4, and 5 exhibit very strong photoluminescence properties and with long lifetimes in the solid state at room temperature.

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A neutral mononuclear FeIII complex [FeIII(H‐5‐Br‐thsa‐Me)(5‐Br‐thsa‐Me)]⋅H2O (1; H2‐5‐Br‐thsa‐Me=5‐bromosalicylaldehyde methylthiosemicarbazone) was prepared that exhibited a three‐step spin‐crossover (SCO) with symmetry breaking and a 14 K hysteresis loop owing to strong cooperativity. Two ordered intermediate states of 1 were observed, 4HS–2LS and 2HS–4LS, which exhibited reentrant phase‐transition behavior. This study provides a new platform for examining multistability in SCO complexes.