| 摘要: | 在系列一中成功合成出以salicylideneamines或B-enaminoketonates為配位基1a-c，並與boron difluoride (BF2)形成錯合物1a-c-BF2其中1a-c-BF2皆有液晶相的生成，藉由改變中心結構的共振長度以及增加推電子基，來觀察對液晶行為表現及光學性質的影響。並且由化合物1c-BF2 (n = 10)單晶結構可得知，中心的硼原子為四面體，並且兩苯環之間的兩面角為81.3˚，這也導致了化合物1c-BF2大多缺乏液晶相。化合物1b-BF2擁有SmC的桿狀型液晶相而化合物1a-BF2和1c-BF2則為SmA相。三化合物的放光波長在溶液態λmax = 476-541 nm而在固態時其放光則在λmax = 488-550 nm，而化合物1c-BF2在固態時則具有AIEE (Aggregation induced enhanced emission)，可做為一良好的發光材料 。
第二系列成功以B-enaminoketonates作為主體，以不同的連接基做置換並與boron difluoride (BF2)形成錯合物2-3-BF2，其中化合物2b-BF2 (n = 12, m = 2, 3)和2c-BF2並無液晶相產生，而以萘環取代苯環的化合物3b-BF2 (m = 2, 3)和3c-BF2因為擁有較平整的分子平面，分子間的堆疊較好因此可誘導出液晶相。經由偏光紋理圖與powder X-ray diffraction實驗結果判定2a-BF2、2b-BF2 (n = 12, m = 0)、3a-BF2、3b-BF2 (m =2)為SmC桿狀液晶，而3b-BF2 (m =3)和3c-BF2為SmA桿狀液晶。另外從培養出的化合物2a-BF2 (n = 12)單晶探討分子之排列情形與作用力多寡。化合物23-BF2以UV可見光光譜、螢光光譜探討該分子的光學性質，從結果可得知中心結構以苯環或者直接相連接時，因延伸其共振使得最大的放光波長紅移，即 max = 523 (2a-BF2), 518 (2b-BF2 (m = 0)), 538 (3a-BF2)。放光為黃綠色光。;In the first part, Three new families of borondifluoride complexes 1a-c-BF2 derived from salicylideneamines 1a and B-enaminoketonates 1b-c were reported, and their mesomorphic and optical properties were also investigated. One single crystal and molecular structure of nonmesogenic BF2 complex 1c-BF2 (n = 10) was resolved and the geometry of the central boron atom was tetrahedron. A larger dihedral angle of 81.3˚ between the two phenyl rings observed in crystal lattice was contributed to the lack of liquid crystallinity. Boron complexes 1a-BF2 formed monotropic SmA phases, while boron complexes 1b-BF2 exhibited enantiotropic SmC mesophases. The optical property of the boron complexes was dependent on their molecular structures, and they emitted a blue-to-green emission at max = 476-541 nm in the solution and 488-550 nm in the solid state. The
1c-BF2 have the property of AIEE (Aggregation-induced enhanced emission), and it can be a protential material of luminescence. In the second part, two new series of bis-(boron difluoride) complexes 2-3-BF2 derived from substituted B-enaminoketonates 2-3 were reported, and their mesomorphic and optical properties were also investigated. 2b-BF2 (n = 12, m = 2, 3) and 2c-BF2 were not mesogens. The single crystal of mesogenic boron complex 2a-BF2 (n = 12) was obtained, and its single crystal and molecular structures were resolved. Results appeared that bis-(BF2) complexes 2a-BF2, 2b-BF2 (n = 12, m = 0), 3a-BF2 and 3b-BF2 (m =2) exhibited smectic C phases. However, 3b-BF2 (m =3) and 3c-BF2 exhibited smectic A phases. In the result, the emission of 2a-BF2, 2b-BF2 and 3a-BF2 red shift to 523, 518 and 538 nm respectively because of their resonance structure. Also, their colors of emission are yellow-green. |
