Complexes of new Schiff base ligands generated in situ from the reaction of 1-aminoglycerol, aldehydes, and metal ions are reported. [Cu4(HL(1))4] (1) and [Ni4O(HL(1))3(H2O)3)]⋅6 H2O⋅DMF⋅DMSO (2) have M4O4 cubane cores, with the L/M molar ratios of 4:4 and 3:4, respectively. [Mn(III)3Mn(II)NaOCl4(HL(1))3]⋅3 MeCN (3) has a unique pentanuclear trigonal propeller-shaped Mn(III)3Mn(II)Na core structure, and the coordination assemblies are linked by hydrogen bonds to afford a 3D channel structure. [Cu2(HL(2))2] (4) has a bis(μ2-alkoxo)-bridged Cu2O2 core, with the binuclear species linked by hydrogen bonds to afford a 1D double-chain. [Ni7(OH)2(OCH3)4(H2L(3)2(MeOH)2(H2O)2]-(ClO4)2⋅10 H2O (5) has a heptanuclear structure containing heptadentate di-Schiff base ligands, with the nickel(II) ions bridged by phenoxo, alkoxo, hydroxo, and methoxo groups to afford a very rare face-sharing hexadruple defective cubane core with a Ni@Ni6 arrangement. The lattice water molecules are linked by hydrogen bonds to form helical chains, which are further hydrogen-bonded to the coordination moieties to afford a 2D network. Variable temperature magnetic susceptibility measurements and nonlinear data-fitting revealed that the "2+4" type of cubane complex 1 shows medium intradimeric ferromagnetic interactions and weak interdimeric ferromagnetic interactions. For complexes 2 and 5, coexistent ferro- and antiferromagnetic couplings afford a non-zero spin ground state. However, compound 3 shows antiferromagnetic interactions between Mn(III) and Mn(II) , and ferromagnetic interactions between the Mn(III) centers, resulting in a global antiferromagnetic behavior. In conclusion, the reaction of 1-aminoglycerol with aldehydes and metal salts afforded polynuclear complexes with a rich structural diversity and remarkable magnetic behavior.

The design and syntheses of porphyrin-based ligands are attractive for creating coordination assemblies with novel structures and intriguing properties. In this work, we designed and synthesized a novel porphyrin-based ligand 5,10,15,20-tetrakis(4,4′-dipyridylaminophenylene)porphyrin (TDPAP, H 2 L) by the introduction of four peripheral 4,4′dipyridylamine moieties to a porphyrin platform. Starting from this novel ligand, the protonated form of the ligand 5) were synthesized. Single crystal X-ray diffraction analyses revealed that a rich structural diversity was observed for these compounds due to the coordination of the multiple peripheral pyridines as well as the porphyrin core. 1 displays a hydrogen bonded one-dimensional (1D) structure composed of [(H 2 O) 2 Cl 2 ] 2− moieties. Complex 2 shows interpenetrated two-dimensional (2D) coordination networks, which are further linked by π•••π stacking interactions to afford a three-dimensional (3D) structure. 3 shows a 2D sheet composed of 50-and 70-membered metallomacrocycles. In complex 4, 1D zigzag coordination chains were generated and further linked to form a 2D structure. Complex 5 has a stairlike 2D structure formed by the linkage of 1D coordination chains through the bridging of binuclear [Cd 2 (CO 2 ) 4 ] subunits. In these compounds, TDPAP shows a unique coordination behavior. It may bind 4−7 metal centers, and it demonstrates conformational flexibility and the ability to form intermolecular hydrogen bonds and π•••π interactions, which contribute to the formation of novel supramolecular structures. On the basis of the novel structures, the solid state emissions of the compounds were also investigated.

Mono-, Tetra-and octanuclear transition metal complexes of in situ generated schiff base ligands containing up to 12 coordinating atoms: syntheses, structures and magnetism{ By the reaction of an alkoxyl containing tetraamine, 1,3-bis[(2-aminoethyl)amino]-2-propanol, with various aldehydes, O-vanillin and 2,6-diformyl-4-cresol, in the presence of various metal cations, four novel complexes were synthesized and structurally characterized. Complexes [CoHL 1 ](ClO 4 )?2MeOH(1) and [NiH 2 L 2 ](ClO 4 ) 2 ?0.5MeOH (2) have mononuclear structures, with the linear di-Schiff base ligand (HL 1 ) 22 and mono-Schiff base ligand H 2 L 2 generated from in situ reactions under various pH conditions. In complexes [Ni 4 L 3 (SCN) 3 (MeOH)]Cl?2.5MeOH (3), and [Cu 8 (H 2 L 3 ) 2 (OH) 4 (ClO 4 )](SCN) 6 (ClO 4 )?8H 2 O (4), an interesting 32-membered dodecadentate macrocyclic ligand H 4 L 3 comprising four Schiff base CLN double bonds was generated by a ''2+2'' type condensation reaction between the tetraamine and the dialdehyde. Complex 3 has a tetranuclear Ni 4 coordination structure with all 12 coordinating atoms of (L 3 ) 42 utilized for coordination, and the alkoxyl groups are deprotonated and coordinated in a bridging mode. Complex 4 exhibits an octanuclear Cu 8 coordination structure, with a ClO 4 2 bridging two tetranuclear [Cu 4 H 2 L 3 (OH) 2 ] 4+ moieties through four weak axial Cu-O coordination bonds. In complex 4, only 10 coordinating atoms of (L 3 ) 42 are utilized for coordination, with the two alkoxyl groups left neutral and noncoordinated. It is noteworthy that H 4 L 3 has two long saturated chains in the molecule. Therefore, it has good flexibility and tends to have a nonplanar structure. Variable temperature magnetic data for 3 and 4 indicated the existence of antiferromagnetic interactions, which were discussed based on the structural results. { Electronic supplementary information (ESI) available: X-ray Crystallographic files (CIF format), selected bond lengths and angles for complexes and magnetic exchange pathways for 4. CCDC reference numbers 886465-886468. See

Eight novel coordination polymers were obtained by the coordination of a multipyridyl and pyrazolyl ligand, which shows rich conformational changes.

The design and syntheses of novel ligands are essential for developing coordination compounds with novel structures and interesting properties. In this work, we designed a n d s y n t h e s i z e d a n o v e l l i g a n d b i s ( 4 , 4 ′dipyridylaminophenylene)butadiyne (L) by attaching two 4,4′dipyridylamine moieties to a flexible butadiyne linker. Starting from this novel ligand, seven coordination polymers [Zn 2 L-(HCOO) 3 7) were synthesized. Single-crystal X-ray diffraction analyses revealed that two forms of the ligand crystals, L and L•0.5DMF present straight and bent conformations, respectively, because of the flexibility of the butadiyne unit. A rich structural diversity was observed for its d 10 metal complexes. Complexes 1 and 5 present ladder-like structures. In complexes 2 and 4, the ligand molecules are linked by metal atoms to afford 3D supramolecular structures. It is noteworthy that the 3D structure of complex 4 consists of interesting infinite {Cd 6 (SO 4 ) 6 } ∞ chains, whereas complexes 3, 6, and 7 exhibit 2D network structures. Interestingly, in the crystal of complex 7, each ligand links four metal ions and each Ag ion bridges two ligands, leading to the formation of undulated 2D sheets with large cavities composed of 66-membered metallomacrocycles, which are interpenetrated by three other such 2D sheets, affording a 4-fold interpenetrated structure. In summary, the complex structures are dependent on the metal ions and the anions. In addition, the flexibility of the butadiyne moiety provides additional means for modulating the structures. Solid state photoluminescence of the free ligand and the complexes shows emission maxima within the range of 420−515 nm, which can be modulated by the conformations of the ligand in addition to the variation of the metal ions and anions, and the introduction of the butadiyne unit has a bathochromic effect.