CAJ | 학술논문

采用水热合成法合成了一种结构新颖的多硼钒氧簇化合物（H2dap）6 H[V12 B16 O54（OH）4]·12H2 O （dap＝1，2-diaminopropane），对化合物1进行了单晶 X 射线衍射，结果表明化合物1属于单斜晶系，C2／c 空间群，晶胞参数 a ＝19．027（4），b ＝16．142（3），c ＝26．679（5），α＝90°，β＝101．06（3）°，γ＝90°， V ＝8042（3）nm3，Z ＝4，Dc ＝1．962 g·cm－3，μ＝1．456 mm－1，F（000）＝4776，7635个可观察独立衍射点射点[I ＞2σ（I ）]，最后结构精修到偏离因子 R1＝0．0626，wR 2＝0．1927，S ＝1．003。该化合物的结构主要由 V12 B16簇单元和作为抗衡离子的1，2-丙二胺组成，且簇单元之间通过强氢键 N—H…O 和弱氢键 C—H…O 的作用连接成了二维的层状结构，层与层之间也是通过氢键的作用连接成了三维的超分子结构。此外，对化合物1进行了红外光谱、磁微扰下的二维红外相关光谱、热微扰下的二维红外相关光谱以及紫外-可见固体漫反射光谱分析的表征，探讨了化合物1的结构与谱学性质的关系。红外光谱表明νas （V—Oμ）反对称伸缩振动吸收峰和νs （V—Oμ）对称伸缩振动吸收峰分别出现在775和683 cm－1，而 BO3中的ν（B—O）键的振动吸收峰以及 BO4四面体中的δ（B—O）的振动吸收峰分别出现在1350和1050 cm－1，磁微扰的二维红外相关光谱表明 B—O 和 V—O—V 的伸缩振动对于磁场的变化具有敏感的响应峰，热微扰的二维红外相关光谱表明 B—OH，B—O 和 V—O—V 的伸缩振动时热微扰具有敏感的响应峰。
채용수열합성법합성료일충결구신영적다붕범양족화합물（H2dap）6 H[V12 B16 O54（OH）4]·12H2 O （dap＝1，2-diaminopropane），대화합물1진행료단정 X 사선연사，결과표명화합물1속우단사정계，C2／c 공간군，정포삼수 a ＝19．027（4），b ＝16．142（3），c ＝26．679（5），α＝90°，β＝101．06（3）°，γ＝90°， V ＝8042（3）nm3，Z ＝4，Dc ＝1．962 g·cm－3，μ＝1．456 mm－1，F（000）＝4776，7635개가관찰독립연사점사점[I ＞2σ（I ）]，최후결구정수도편리인자 R1＝0．0626，wR 2＝0．1927，S ＝1．003。해화합물적결구주요유 V12 B16족단원화작위항형리자적1，2-병이알조성，차족단원지간통과강경건 N—H…O 화약경건 C—H…O 적작용련접성료이유적층상결구，층여층지간야시통과경건적작용련접성료삼유적초분자결구。차외，대화합물1진행료홍외광보、자미우하적이유홍외상관광보、열미우하적이유홍외상관광보이급자외-가견고체만반사광보분석적표정，탐토료화합물1적결구여보학성질적관계。홍외광보표명νas （V—Oμ）반대칭신축진동흡수봉화νs （V—Oμ）대칭신축진동흡수봉분별출현재775화683 cm－1，이 BO3중적ν（B—O）건적진동흡수봉이급 BO4사면체중적δ（B—O）적진동흡수봉분별출현재1350화1050 cm－1，자미우적이유홍외상관광보표명 B—O 화 V—O—V 적신축진동대우자장적변화구유민감적향응봉，열미우적이유홍외상관광보표명 B—OH，B—O 화 V—O—V 적신축진동시열미우구유민감적향응봉。
A polyoxovanadium borate (H2 dap)6 H[V12 B16 O54 (OH)4 ]·12H2 O(dap=1,2-diaminopropane)with novel structure was hydrothermally synthesized and characterized by the single crystal X-ray diffraction.It crystallizes in triclinic system with space group Pīand unit cell parameters a=19.027(4),b=16.142(3)?,c =26.679(5)?,α=90°,β=101.06(3)°,γ=90°,V=8042(3)?3 ,Z =4,Dc = 1.962 g · cm-3 ,μ= 1.456 mm-1 ,F (000 )=4 776,the final R1 =0.062 6,wR2 =0.192 7, S =1. 003,for 7 635 observed reflectionswith I >2σ(I ).It is showed that the compound 1 is composed of V12 B16 clusters unit and dap which is as a counter ion,and a two-dimensional layered structure is obtained by the effect of hydrogen bonding between the cluster units and dap,and between the layers via strong hydrogen bonds to form a three-dimensional supramolecular struc-ture.The compound 1 were also characterized by IR,two-dimensional infrared (2D IR)correlation spectroscopy with magnetic and thermal perturbation,UV/Vis DRS spectra.The relationship between the structure and spectroscopy properties was dis-cussed.The IR spectrum showed that the antisymmetric stretching vibration absorption peakνas (V—Oμ)and symmetric stretc-hing vibration absorption peaksνs (V—Oμ)appeared at 775 and 683 cm-1 respectively,whereas the vibration absorption peak inν(B—O)of BO3 and the vibration absorption peak inν(B—O)of BO4 appeared at 1 350 and 1 050 cm-1 respectively.The re-sponse of the stretching vibrations of B—O and V—O was detected in the 2D IR correlation spectra with magentic perturba-tion. In addition,the response of the stretching vibrations of B—OH,B—O and V—O—V was detected in the 2D IR correlation spec-tra with thermal perturbation.