无机化学学报
無機化學學報
무궤화학학보
JOURNAL OF INORGANIC CHEMISTRY
2007年
12期
2059-2064
,共6页
张艳斌%鞠艳玲%李艳秋%李夏
張豔斌%鞠豔玲%李豔鞦%李夏
장염빈%국염령%리염추%리하
镝%二甘醇酸%配位聚合物%晶体结构%荧光
鏑%二甘醇痠%配位聚閤物%晶體結構%熒光
적%이감순산%배위취합물%정체결구%형광
dysprosium%diglycolic acid%coordination polymer%crystal structure%fluorescence
DyCl3·6H2O与二甘醇酸(H2dga)在水热条件下反应得到配位聚合物{[Dy2(dga)3(H2O)4]·2H2O}n,用X-射线衍射单晶结构分析方法确定了其晶体结构.该配合物的晶体属于正交晶系,C2221空间群.在配合物中,Dy3+离子存在两种类型的配位环境.九配位的Dy1离子与3个二甘醇酸根的6个羧基氧原子和3个醚氧原子配位,其配位多面体可描述为一个扭曲的单帽四方反棱柱;八配位的Dy2离子周围的8个配位氧原子形成一个扭曲的四方反棱柱配位多面体,其中4个氧原子来自4个二甘醇酸根,另外4个氧原子由4个配位水分子提供.二甘醇酸配体的2个羧基和其醚氧原子同时与Dy3+离子配位而形成2D网状结构.该配合物在室温下的固体荧光光谱显示了中心Dy3+离子的特征荧光,位于483 nm和574 nm的发射峰分别对应于Dy3+离子的4F9/2→6H15/2和4F9/2→6H13/2跃迁.
DyCl3·6H2O與二甘醇痠(H2dga)在水熱條件下反應得到配位聚閤物{[Dy2(dga)3(H2O)4]·2H2O}n,用X-射線衍射單晶結構分析方法確定瞭其晶體結構.該配閤物的晶體屬于正交晶繫,C2221空間群.在配閤物中,Dy3+離子存在兩種類型的配位環境.九配位的Dy1離子與3箇二甘醇痠根的6箇羧基氧原子和3箇醚氧原子配位,其配位多麵體可描述為一箇扭麯的單帽四方反稜柱;八配位的Dy2離子週圍的8箇配位氧原子形成一箇扭麯的四方反稜柱配位多麵體,其中4箇氧原子來自4箇二甘醇痠根,另外4箇氧原子由4箇配位水分子提供.二甘醇痠配體的2箇羧基和其醚氧原子同時與Dy3+離子配位而形成2D網狀結構.該配閤物在室溫下的固體熒光光譜顯示瞭中心Dy3+離子的特徵熒光,位于483 nm和574 nm的髮射峰分彆對應于Dy3+離子的4F9/2→6H15/2和4F9/2→6H13/2躍遷.
DyCl3·6H2O여이감순산(H2dga)재수열조건하반응득도배위취합물{[Dy2(dga)3(H2O)4]·2H2O}n,용X-사선연사단정결구분석방법학정료기정체결구.해배합물적정체속우정교정계,C2221공간군.재배합물중,Dy3+리자존재량충류형적배위배경.구배위적Dy1리자여3개이감순산근적6개최기양원자화3개미양원자배위,기배위다면체가묘술위일개뉴곡적단모사방반릉주;팔배위적Dy2리자주위적8개배위양원자형성일개뉴곡적사방반릉주배위다면체,기중4개양원자래자4개이감순산근,령외4개양원자유4개배위수분자제공.이감순산배체적2개최기화기미양원자동시여Dy3+리자배위이형성2D망상결구.해배합물재실온하적고체형광광보현시료중심Dy3+리자적특정형광,위우483 nm화574 nm적발사봉분별대응우Dy3+리자적4F9/2→6H15/2화4F9/2→6H13/2약천.
A new lanthanide coordination polymer {[Dy2(dga)3(H2O)4]·2H2O}n was prepared by hydrothermal method with DyCl3·6H2O and diglycolic acid (H2dga), and structurally characterized by single-crystal X-ray diffraction technique. The complex crystallizes in Orthorhombic system, C2221 space group with a=1.773 5(11) nm, b =0.875 2(6) nm, c=1.504 3(9) nm, V=2.335 0(3) nm3, Dc=2.359 Mg·m-3, Z=4,μ=6.447 mm-1, F(000)=1 584.0, R=0.0507, wR=0.121 6. In the complex, there are two types of coordination environments for Dy3+ ion. One Dy1 ion is nine-coordinated by three diglycolato groups via six carboxyl oxygen atoms and three ether oxygen atoms. The Dy1 ion is in a distorted monocapped square-antiprism coordination geometry. Whereas the other Dy2 ion is eight-coordinated and the coordination sphere around each Dy2 ion consists of four carboxyl oxygen atoms from four diglycolato ligands and four oxygen atoms from four coordinated water molecules. The coordination polyhedron of Dy2 ion can be described as a distorted square-antiprism. Eight- and nine-coordinate Dy3+ ions are linked by diglycolato ligands to form a 2D network structure. The fluorescence spectral of the complex in solid state at room temperature shows that the diglycolic acid is suitable for the sensitization on the luminescence of Dy3+ ion. CCDC: 660435.