| Borates are not only rich in structures,but also have wide applications in nonlinear optical properties,mineralogy.Recently,exploration of borates with new compositions and structures has become hot.Under hydrothermal conditions,organic amines or metal complexes have a significant structure-directing effect on the formation of novel frameworks,which can be functionalized for targeted applications.In this paper,a series of borates have been made under hydro/solvothermal conditions.The structure was determined by single crystal X-ray diffraction and further characterized by elemental analysis,FT-IR,thermogravimetric analysis and photoluminescence spectroscopy.We also examine their SHG property of noncentrosymmetric structure crystals.We get two types of compounds:1.Aluminoborates with open-frameworksSeven aluminoborates containing one organic and six metal-organic complex tem-plated aluminoborates were made under hydro/solvothermal conditions.?NH3CH2CH2NH2??NH3CH2CHNH2CH3?[AlB5O10]?3-1?[Zn?1,2-dap?2][AlB5O10]?3-2?Cd?1,2-dap?2AlB7.5O13?OH?2·0.5H3O?3-3?Zn?1,2-dap?2AlB7.5O13?OH?2·0.5H3O?3-4?Cd0.5?1,2-dap?{Cd?1,2-dap?2Al[B5O8?OH?2]2}?3-5?Zn?en?2Al[B5O9?OH?][BO?OH?2]?3-6?Cd?en?2AlB5O10·0.5H2O?3-7?Compound 3-1 was synthesized co-templated by two types of primary amines under solvothermal conditions.The alternate connectivity between the B5O10 clusters and the AlO4 tetrahedra by their vertices result in the formation of the final 3D framework with intersecting 10-,11-,11-MR channels along the[110],[010]and[001]directions.The topology of the 3D framework can be simplified by considering the AlO4 tetrahedra and the B5O10 clusters to be four-connected nodes.Compound 3-1 exhibit good SHG response of?1.3 times that of KDP?KH2PO4?powder.With transition metal complexes as the structure-directing agents,a 3D open-framework 3-2 has been solvothermally prepared.The AlO4 groups and B5O10 clusters alternately link together to form a 3D framework,in which the stacking of building layers is different.3-3,3-4 are isostructural.Both left-handed and right-handed helices exist in the structure.The layers have helical channels with 8MR and 6MR in the[010]direction.Along the[100]direction,there are two spiral channels with 8MR.Compound 3-5 was synthesized by transition metal complexes.Each AlO4 group is connected to four others through four bridging B5O8?OH?2 clusters,whereas each B5O8?OH?2 cluster is connected to six others through two AlO4 groups,forming an unprecedented 4,6-connectivity in ABOs.Compound 3-5 incorporate two Cd-1,2-dap complexes which act as templates or directly bond to the walls of borate.3-6 is a 2D layer constructed by the alternate linkages of AlO4groups and B5O9?OH?clusters,then further held together via H-bonding interactions.SHG measurements revealed that 3-6 exhibits a moderate SHG response about 3.3 times that of KDP?KH2PO4?powder.Single crystal X-ray analysis indicates that 3-7 crystallizes in the orthorhombic space group P2?1?2?1?2?1?.Its host anionic[Al(B5O10)]n2n-framework is based on the alternate linkage of AlO4 tetrahedra and B5O10 units via corner-sharing.2.Zincoborates[Zn?dap?3][Zn?dap?B5O8?OH?2]2?4-1?Compound 4-1 consists of one-dimensional?1-D?helical chains built up from[B5O8?OH?2]clusters and Zn complex linkers.The H-bonding interactions between adjacent chains lead to 3-D supramolecular network structure. |
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