A trial manufacture of irradiation/photometry system for cryogenic magneic susceptometer and optofunctionalization of molecule based magnet

低温磁感受器辐照/测光系统的试制及分子磁体的光功能化

• 批准号: 08554023
• 负责人: IWAMURA Hiizu
• 金额: $ 9.86万
• 依托单位: KYUSHU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08554023/
• 关键词: SQUID susceptometer; Nd; YAG laser; Second harmonic dipyridylcarbene; dipyridylcarbene; YAGレーザー

By mixing 4,4-dipyridyldiazomethane with Mn (hfac) _2or Cu (hfac) _2in 1 : 1 ratio, 1 : 1 complexes have been obtained as red-orange and dark green crystals respectively. X-ray crystallography revealed the polymorphism of the manganese complex. While in one crystal pyridine coordinated as cis configuration and resulted in helical structure, in the other crystal the structure was trans configuration and zigzag chain. Copper complexes had trans configuration and zigzag chain. The photolysis to the crystal was performed by second harmonic wave of Nd/YAG laser. The magnetic susceptibility before and after photolysis was measured by SQUID susceptometer at 2-300K.The temperature dependence of the susceptibility of manganese complex before irradiation showed isolation of magnanese spin, but after irradiation the formation of ferrimagnetic one-dimensional chain composed of manganese and carbene spins. The maximun number of correlation spins was 900. In the case of copper complex, ferromagnetic one-dimensional chain was formed.

将4，4-联吡啶重氮甲烷与Mn（hfac）_2或Cu（hfac）_2按1：1的比例混合，得到1：1的配合物，分别为红橙色和深绿色晶体。X射线晶体学显示锰配合物的多晶型。其中一种晶体中吡啶以顺式配位形成螺旋结构，而另一种晶体中吡啶以反式配位形成锯齿状链状结构。铜配合物具有反式构型和锯齿形链状结构。用Nd/YAG激光的二次谐波对晶体进行光解。在2- 300 K温度范围内，用SQUID磁敏仪测量了锰配合物光解前后的磁化率，发现锰配合物在辐照前磁化率随温度的变化表现为锰自旋的孤立，而在辐照后形成了由锰和卡宾自旋组成的亚铁磁一维链.最大相关自旋数为900。在铜配合物的情况下，铁磁一维链形成。

项目成果

Kenji Matsuda: "Control of the “Superexchenge" Interaction through Diphenyl Sulfide 4,4-Diyl Magnetic Coupler by Changing the Oxidation State and Conformation of the Sulfur Atom" J.Am.Chem.Soc.119. 8058-8064 (1997)

Kenji Matsuda：“通过改变硫原子的氧化态和构象来控制二苯硫醚 4,4-二基磁耦合剂的“超级交换”相互作用”J.Am.Chem.Soc.119 (1997)。

Hiizu Iwamura: "High-Spin Polynitroxide Radicals as Versatile Bridging Ligands for Transition Metal Complexes with High-Ferri-/Ferromagnetic TC" Pure Appl.Chem.68. 243-252 (1996)

Hiizu Iwamura：“高自旋聚硝基氧自由基作为具有高铁/铁磁性 TC 的过渡金属配合物的多功能桥连配体”Pure Appl.Chem.68。

K.Matsuda and H.Iwamura: ""High-spin Organic Molecular Materials"" Curr.Opin.Solid State Mater.Sci.2(4). 446-450 (1997)

K.Matsuda 和 H.Iwamura：““高自旋有机分子材料””Curr.Opin.Solid State Mater.Sci.2(4)。

H.Iwamura, K.Inoue and T.Hayamizu: ""High-Spin Polynitroxide Radicals as Versatile Bridging Ligands for Transition Metal Complexes with High Ferri-/Ferromagnetic Tc"" Pure Appl.Chem.68. 243-252 (1996)

H.Iwamura、K.Inoue 和 T.Hayamizu：“高自旋聚硝基氧自由基作为具有高铁/铁磁性 Tc 的过渡金属配合物的通用桥配体””Pure Appl.Chem.68。

J.Fujita, M.Tanaka, H.Suemune, N.Koga, K.Matsuda, and H.Iwamura: ""Antiferromagnetic Exchange Interaction among the Three Spins Placed in an Isosceles Triangular Configuration in 2,4-Dimethoxy-1,3,5-benzenetriyltris (N-tert-butyl nitroxide) "" J.Am.Chem.S

J.Fujita、M.Tanaka、H.Suemune、N.Koga、K.Matsuda 和 H.Iwamura：“2,4-二甲氧基-1,3 中等腰三角形构型的三个自旋之间的反铁磁交换相互作用”