周边硅笼取代的混杂酞菁卟啉三层铽单分子磁体

通过在铽的酞菁卟啉混杂三层的卟啉周边共价连接体积庞大的笼型倍半硅氧烷(POSS), 得到了首个包含POSS的混杂三层Tb₂(Pc)[T(OPOSS)₄PP]₂ (1)[H₂Pc=phthalocyanine;H₂T(OPOSS)₄PP=5, 10, 15, 20-tetra{[[N-[heptakis(isobutyl)propoxy]phenyl]octasiloxane]}porphyrin]。为了对比研究, 同时合成了类似的三层化合物Tb₂(Pc)(TPP)₂(2)(H₂TPP=5,10,15,20-tetraphenyporphyrin)。尤其值得注意的是, 在没有外加磁场的条件下, Tb₂(Pc)[T(OPOSS)₄PP]₂(1)和Tb₂(Pc)(TPP)₂(2)分别表现出单分子磁体和非单分子磁体的性质, 这充分说明了共价连接均匀分布的POSS基团有效地分离了磁性核心, 从而改善了酞菁卟啉混杂三层的磁性。     

六种酞菁锌配合物：交叉聚合法合成、分离、光谱和电化学性质

使用2种前驱体1和2(1=4,5-二(4-甲酯基)酚氧取代邻苯二甲腈,2=4-二缩三乙二醇单甲醚取代邻苯二甲腈)与Zn(OAc)₂·2H₂O在DBU(1,8-二氮杂双环[5.4.0]十一碳-7-烯)催化下,在正戊醇中进行酯交换及交叉聚合反应得到6种酞菁锌配合物。通过简单的硅胶柱色谱,可以将这6种配合物Zn[Pc(BP)₄](3),Zn[Pc(BP)₃(TEG)](4),Zn[Pc(BP)₂(TEG)₂]-opp(5),Zn[Pc(BP)₂(TEG)₂]-adj(6),Zn[Pc(BP)(TEG)₃](7)和Zn[Pc(TEG)₄](8)进行分离。对合成的6种化合物进行了质谱,元素分析,紫外-可见吸收光谱,核磁共振谱表征。另外,对这些化合物的电化学性质也进行了研究。     

基于席夫碱配体和两种苯甲酸盐构筑的两例Dy4配合物的合成、结构及单分子磁体性质

使用Dy(NO₃)₃·6H₂O与席夫碱配体2-(((2-羟基-3-甲氧基苄基)亚氨基)甲基)-4-甲氧基苯酚(H₂L)和2个辅助配体PhCO₂H和2-NO₂-PhCO₂H在乙醇中反应,得到2例Dy₄配合物[Dy₄(L)₄(PhCO₂)₂(NO₃)₂(EtOH)₂](1)和[Dy₄(L)₄(2-NO₂-PhCO₂)₂(NO₃)₂(EtOH)₂](2)。单晶X射线衍射解析表明配合物1和2均由Dy₂基本单元构建,形成中心对称的四核线性链状结构。配合物1和2中Dy₂单元中的一个Dy(Ⅲ)离子呈现七配位几何构型,另一个Dy(Ⅲ)离子呈现八配位几何构型。2例配合物均为单分子磁体,其能垒分别为110和108 K。通过理论计算对1和2的磁性能进行了分析。     

基于席夫碱配体和两种苯甲酸盐构筑的两例Dy4配合物的合成、结构及单分子磁体性质

使用Dy (NO₃)₃·6H₂O与席夫碱配体2-(((2-羟基-3-甲氧基苄基)亚氨基)甲基)-4-甲氧基苯酚(H₂L)和2个辅助配体PhCO₂H和2-NO₂-PhCO₂H在乙醇中反应,得到2例Dy₄配合物[Dy₄(L)₄(PhCO₂)₂(NO₃)₂(EtOH)₂](1)和[Dy₄(L)₄(2-NO₂-PhCO₂)₂(NO₃)₂(EtOH)₂](2)。单晶X射线衍射解析表明配合物1和2均由Dy₂基本单元构建,形成中心对称的四核线性链状结构。配合物1和2中Dy₂单元中的一个Dy (Ⅲ)离子呈现七配位几何构型,另一个Dy (Ⅲ)离子呈现八配位几何构型。2例配合物均为单分子磁体,其能垒分别为110和108 K。通过理论计算对1和2的磁性能进行了分析。     

篮子型有机膦酸锰簇合物：合成、晶体结构与磁性质研究

本文报道了1个新的有机膦酸锰簇合物[Mn₅O₃(C₁₁H₉PO₃)₂(PhCOO)₅(phen)₂]·2H₂O (1)的合成、结构及磁性质。单晶结构分析显示化合物1含有[Mn₅O₃]⁹⁺核结构,该结构通过连接5个金属离子形成了篮子型簇结构。化合物1的直流磁化率测试表明金属离子之间存在反铁磁相互作用。交流磁化率测试没有发现实部和虚部出现频率依赖行为,说明化合物1不是一个单分子磁体。     

镍螺旋化合物及其杂银配位聚合物的设计合成与结构

采用两个易扭转异构的双三齿有机配体，双吡啶二甲基-6,6′-二酰肼-2,2′-连吡啶(H₂L¹)和双吡啶二乙基-6,6′-二酰肼-2,2′-连吡啶(H₂L²)，和金属镍离子组装得到2个金属螺旋体(helicate)，Ni₂(HL¹)₂(PF₆)(BF₄)(CH₃OH)(H₂O)₂ (1)和Ni₂(HL²)(H₂L²)(ClO₄)₃(C₂H₅OH)(CH₃OH)H₂O)₃ (2),并测定了它们的晶体结构。同时由配体H₂L³出发,通过逐级组装的方法,得到一个镍-银杂金属的配位聚合物Ni₂Ag₂(HL³)₂(ClO₄)₂(CH₃CN)₃ (3)。单晶结构表明，配位聚合物3中配体H₂L³首先与镍离子组装成分子盒化合物(molecular box)，该结构单元进一步通过Ag离子与分子盒外围N原子配位，使分子盒互相串连成一维配位聚合物3，分子盒聚集体沿c方向伸展成一维链结构，链与链之间相互平行，进一步堆积成二维孔道结构。     

以还原型钼磷酸盐[P4MoV6O28(OH)3]9-为建筑单元构筑新型多维延展结构材料

向MoO₃, H₃PO₄和bpy(4,4′-bipyridine)组成的反应体系中分别引入Cd(OAc)₂·2H₂O 和MnCl₂·4H₂O, 在水热条件下合成了两种基于还原型钼磷酸盐[P₄Mo₆O₂₈(OH)₃]^9-(简称{P₄Mo₆})为建筑单元构筑的新型多维延展型无机-有机杂化材料(H₂bpy)₂[Cd(H₂O)]₃[Cd(HPO₄)₆(PO₄)₂(OH)₆(MoO₂)₁₂]·5H₂O(1)和 (H₂bpy)₃[Mn(H₂O)₂]₂ [Mn(HPO₄)₆(PO₄)₂(OH)₆(MoO₂)₁₂]·10H₂O(2), 并通过元素分析、红外光谱、热重分析和X射线单晶衍射对其进行了表征。结果表明, 化合物1和2均属于三斜晶系, P1 空间群。化合物1的阴离子[Cd(H₂O)]₃[Cd(HPO₄)₆(PO₄)₂(OH)₆(MoO₂)₁₂]^2-是由二聚体 Cd[P₄Mo₆]₂通过{Cd₃}簇依次连接形成的一维无机链状结构; 化合物2的阴离子[Mn(H₂O)₂]₂[Mn(HPO₄)₆(PO₄)₂(OH)₆(MoO₂)₁₂]^3-则是由二聚体Mn[P₄Mo₆]₂通过Mn²⁺离子连接形成的二维无机层状结构。这2种无机延展结构均同质子化的bpy通过氢键作用形成不同的三维超分子网络。同时还探讨了化合物2的电化学性质。     

原位羟基化2，2′-联吡啶类配体及其新颖的铜(Ⅰ)和混价铜(Ⅰ，Ⅱ)超分子构筑的合成(英)

本文利用水热法合成了两个新型一价铜配合物[Cu₂(ophen)₂]·H₂O的类同质多晶结构（1α和1β）和一个混合价的铜配合物[Cu₂(obpy)₂(NO₃)]·H₂O (2)。晶体结构分析表明：1α显现出于无水的类似物[Cu₂(ophen)₂]相同的堆积方式，1β则形成出新奇的空间堆积。混合价化合物2是完全离域的，通过氢键集聚体[(H₂O)₂(NO₃^-)₂]将两个[Cu₂(obpy)₂]⁺单元连接起来形成哑铃状的四核结构。     

基于2-甲基-8-羟基喹啉的镝单分子磁体的晶体结构及磁性

以2-甲基-8-羟基喹啉(HL)为配体合成了2个含有镝离子的配位化合物[Dy₂L₄(HL)₄(H₂O)₂](ClO₄)₂·2H₂O(1)和[Dy₂L₆(C₂H₅OH)]·H₂O(2)。虽然在这两个配位化合物中配体都是2-甲基-8-羟基喹啉,但其参与配位的方式不同。这导致2个化合物中镝离子所处的配位环境不同,进而对化合物的磁性产生了影响。     

2,7-萘二磺酸阴离子导向五元瓜环基超分子自组装体的制备及其荧光检测性能

通过引入2,7-萘二磺酸(2,7-NDA^2-)阴离子作为结构导向剂,与五元瓜环(Q[5])和过渡金属离子(Co²⁺、Ni²⁺、Zn²⁺、Cd²⁺)在水热条件下制备了4种新颖的Q[5]基超分子自组装体(Q[5]-SA),即{[M (H₂O)₄(Q[5])]·(NDA)}·xH₂O (M=Co (1)、Ni (2)、Zn (3))和{[Cd₂Cl₂(H₂O)₄(Q[5])]·(NDA)}·13H₂O (4)。单晶X射线衍射测试结果表明,自组装体1~3同构,其中Q[5]仅一端的部分端口羰基氧原子与金属离子配位形成简单配合物;而4中Q[5]的2个端口均与金属离子Cd²⁺配位形成了一维配位链。在自组装体1~4中,配体2,7-H₂NDA均全脱质子,形成2,7-NDA^2-阴离子平衡体系电荷,但均未能与金属离子配位,而在2,7-NDA^2-阴离子与Q[5]外壁之间的瓜环外壁作用下进一步形成三维超分子结构。此外,还研究了自组装体1和4的荧光传感性能,结果表明它们都能够作为抗生素诺氟沙星(NFX)的比率型荧光探针。     

Manipulation of the Coordination Geometry along the C4 Rotation Axis in a Dinuclear Tb3+ Triple-Decker Complex via a Supramolecular Approach

A supramolecular complex ( 1⋅ C₆₀) was prepared by assembling (C60-Ih)[5,6]fullerene (C₆₀) with the dinuclear Tb³⁺ triple-decker complex [(TPP)Tb(Pc)Tb(TPP)] ( 1 : Tb³⁺=trivalent terbium ion, Pc²⁻=phthalocyaninato, TPP²⁻=tetraphenylporphyrinato) with quasi-D_4h symmetry to investigate the relationship between the coordination symmetry and single-molecule magnet (SMM) properties. Tb³⁺-Pc triple-decker complexes (Tb₂Pc₃) have an important advantage over Tb³⁺-Pc double-decker complexes (TbPc₂) since the magnetic relaxation processes correspond to the Zeeman splitting when there are two 4f spin systems. The two Tb³⁺ sites of 1 are equivalent, and the twist angle (φ) was determined to be 3.62°. On the other hand, the two Tb³⁺ sites of 1⋅ C₆₀ are not equivalent. The φ values for sites Tb1 and Tb2 were determined to be 3.67° and 33.8°, respectively, due to a change in the coordination symmetry of 1 upon association with C₆₀. At 1.8 K, 1 and 1⋅ C₆₀ undergo different magnetic relaxations, and the changes in the ground state affect the spin dynamics. Although 1 and 1⋅ C₆₀ relax via QTM in a zero applied magnetic field (H), H dependencies of the magnetic relaxation times (τ) for H>1500 Oe are similar. On the other hand, for H<1500 Oe, the τ values have different behaviors since the off-diagonal terms ( ) affect the magnetic relaxation mechanism. From temperature (T) and H dependences of τ, spin-phonon interactions along with direct and Raman mechanisms explain the spin dynamics. We believe that a supramolecular method can be used to control the magnetic anisotropy along the C₄ rotation axis and the spin dynamic properties in dinuclear Ln³⁺-Pc multiple-decker complexes.     

Volumetric properties of methyl,tert-butyl, and alkoxy derivatives of tetraphenylporphyrin in benzene solution

Densities, apparent molar volumes, and partial molar volumes of benzene solutions ofmeso-tetradimethylphenyl porphyrin derivatives H₂T(i,j-CH₃)PP (where i,j = 2,3-; 2,4-; 3,4-; 2,5-; 3,5-);meso-tetra-4-alkoxyphenyl porphyrin derivatives H₂T(4-OC_nH_2n+1)PP (wheren = 2–4,6–8,10,12,16);meso-tetra-3-butoxyphenyl porphyrin H₂T(3-OC₄H₉)PP;meso-tetra-4-tert-butylphenyl porphyrin H₂T(4tBu)PP;meso-tetra-3,5-ditert-butylphenyl porphyrin H₂T(3,5-tBu)PP at 25°C and tetraphenylporphyrin, H₂TPP,H₂T(4-OC₁₀H₂₁)PP;H₂T(4-OC₁₂H₂₅)PP and H₂T(4tBu)PP at 20°C; 30°C; 40°C; 50°C were determined. The solubilities of the compounds in benzene at 25°C were measured. The solvent excluded volumes for different conformational states and the topology of dimethyl derivatives of tetraphenylporphyrin were calculated and compared with partial molar volume data. The correlation between the partial molar volumes and van der Waals volumes for the derivatives H₂TPP,n-alkanes,n-alkanols, fatty acids, cyclic compounds, and crown ethers using the equation of Terasawa was elaborated. The average increment of the methylene group for alkoxy-substituted H₂TPP was calculated as δV ₂ ^o (CH₂) = 16.6±0.4cm³-mol^-1. The volumetric expansion coefficients of benzene solutions of H₂TPP; H₂T(4-OC₁₀,H₂₁)PP; H₂T(4-OC₁₂H₂₅)PP and H₂T(4-tBu)PP were determined and discussed. The importance of packing efficiencies around the solute molecules were examined.     

Fourier transform ion cyclotron resonance studies of lanthanide(III) porphyrin-phthalocyanine heteroleptic sandwich complexes by using electrospray ionization

A number of neutral Ianthanide(III) porphyrin-phthalocyanine heteroleptic sandwich complexes have been studied by using positive-ion electrospray ionization-Fourier transform ion cyclotron resonance mass spectrometry. The investigated compounds are represented as Ln^III(TPP)(Pc), Ln ₂ ^III (TPP)(Pc)₂, and Ln ₂ ^III (TPP)₂(Pc), where Ln = Sm, Eu, or Gd, TPP is 5,10,15,20-tetraphenylporphyrinate, and Pc is phthalocyaninate. In all cases, intense signals corresponding to the singly charged molecular radical cations are observed. The formation of these molecular radical cations in electrospray ionization is attributed to electrochemical oxidation at the electrospray needle. Multiply charged molecular ions up to +5 are also observed. They are tentatively assigned to be formed from successive oxidation of the ligand(s). Apart from the molecular weight information, tandem mass spectrometry offers additional structural information on these complexes. From the fragmentation pattern of the europium complexes under collision-induced dissociation conditions, the configurations of the triple-decker complexes are assigned mass spectrometrically to be (TPP)Eu(Pc)Eu(Pc) and (TPP)Eu(Pc)Eu(TPP). In comparison with the previous spectroscopic findings that the positive “hole” is localized in the ligands of the complexes, there is evidence to suggest that intramolecular charge transfer or hole delocalization does occur within the macrocycles or between the metal centers and the macrocycles before fragmentation. The occurrence of this charge-transfer process is tentatively attributed to the result of collisional activation.     

Unsymmetrical Pyrene‐Fused Phthalocyanine Derivatives: Synthesis,Structure, and Properties

Novel pyrene‐fused unsymmetrical phthalocyanine derivatives 2,3,9,10,16,17‐hexakis(2,6‐dimethylphenoxy)‐22,25‐diaza(2,7‐di‐tert‐butylpyrene)[4,5]phthalocyaninato zinc complex Zn[Pc(Pz‐pyrene)(OC₈H₉)₆] ( 1 ) and 2,3,9,10‐tra(2,6‐dimethylphenoxy)‐15,18,22,25‐traza(2,7‐di‐tert‐butylpyrene)[4,5]phthalocyaninato zinc compound Zn[Pc(Pz‐pyrene)₂(OC₈H₉)₄] ( 2 ) were isolated for the first time. These unsymmetrical pyrene‐fused phthalocyanine derivatives have been characterized by a wide range of spectroscopic and electrochemical methods. In particular, the pyrene‐fused phthalocyanine structure was unambiguously revealed on the basis of single crystal X‐ray diffraction analysis of 1 , representing the first structurally characterized phthalocyanine derivative fused with an aromatic moiety larger than benzene.     

Morphology‐Controlled Self‐Assembly of an Organic/Inorganic Hybrid Porphyrin Derivative Containing Polyhedral Oligomeric Silsesquioxane (POSS)

An organic/inorganic hybrid porphyrin derivative, namely, metal‐free tetrakisphenyl porphyrin–polyhedral oligomeric silsesquioxanes (H₂TPP‐POSS) was synthesized by azide–alkyne click chemistry. The self‐assembly behavior of H₂TPP‐POSS was systematically studied in CHCl₃ at different concentrations and in solvents with different polarities. Novel nanovesicles could be obtained through the self‐assembly of H₂TPP‐POSS in CHCl₃ at a concentration lower than 10^?4 m. Diffuse microrods formed at a concentration higher than 10^?4 M . Additionally, the polarity of the solvent also greatly influenced the assembled morphologies, and a series of assembled morphologies, including crescent‐shaped micelles, spherical micelles, doughnut‐shaped vesicles, and ordered square sheets, could form in solvents with different polarities.     

Magnetoresistance Study on TPP[M(Pc)(CN)2]2 (M=Fe, Co, Fe0.30Co0.70) Salts

The magnetoresistance study on TPP[M(Pc)(CN)₂]₂ (M=Fe, Co, Fe_0.30Co_0.70) salts is reported. These three salts have similar columnar structures, nevertheless exhibit different electrical behaviors. TPP[Fe(Pc)(CN)₂]₂ exhibits anisotropic giant negative magnetoresistance, while TPP[Co(Pc)(CN)₂] exhibits large positive magnetoresistance. The alloyed compound, TPP[Fe_0.30Co_0.70 (Pc)(CN)₂]₂, also exhibits anisotropic negative magnetoresistance, although the decrease in the resistivity under the magnetic field is less than that of TPP[Fe(Pc)(CN)₂]₂. The g-tensor anisotropy in the [Fe(Pc)(CN)₂] unit qualitatively explains the field-orientation dependence of the negative magnetoresistance. Magnetic fluctuation associated with a weak-ferromagnetic transition is suggested as a possible origin of the giant negative magnetoresistance.     

Ligand exchange in the complexone-porphyrin macrocycle system in reactions of copper(II) ethylenediaminetetraacetate with porphyrins and phthalocyanines

Complexation between 5,10,15,20-tetraphenylporphine H₂TPP and tetra(tert-butyl)phthalocyanine H₂(t-Bu)₄Pc with copper(II) ethylenediaminetetraacetate in DMSO was studied by spectrophotometry. The kinetic parameters of the reaction were calculated and the mechanism of ligand exchange in the complexone-porphyrin macrocycle system was proposed. The reactivities of H₂TPP and H₂(t-Bu)₄Pc in reactions with copper ethylenediaminetetraacetate and some other copper chelate complexes were compared.     

The molecular structure of high‐spin (S = ) manganese(II) phthalocyanine in tetrabutylammonium bromido(phthalocyaninato)manganese(II)

The title complex salt, (C₁₆H₃₆N)[MnBr(C₃₂H₁₆N₈)] or (TBA)[Mn^IIBr(Pc)] (TBA is tetrabutylammonium and Pc is phthalocyaninate), has been obtained as single crystals by the diffusion technique and its crystal structure was determined using X‐ray diffraction. The high‐spin (S = ) [Mn^IIBr(Pc)]⁻ macrocycle has a concave conformation, with an average equatorial Mn—N(Pc) bond length of 2.1187 (19) Å, an axial Mn—Br bond length of 2.5493 (7) Å and with the Mn^II cation displaced out of the 24‐atom Pc plane by 0.894 (2) Å. The geometry of the Mn^IIN₄ fragment in [Mn^IIBr(Pc)]⁻ is similar to that of the high‐spin (S = ) manganese(II) tetraphenylporphyrin (TPP) in [Mn^II(1‐MeIm)(TPP)] (1‐MeIm is 1‐methylimidazole).     

Methyloxy Substituted Heteroleptic Bis(phthalocyaninato) Yttrium Complexes: Density Functional Calculations

The effects of alkyloxy substituents attached to one phthalocyanine ligand of three heteroleptic bis(phthalocyaninato) yttrium complexes Y(Pc)[Pc(α‐OCH₃)₄] ( 1 ), Y(Pc)[Pc(α‐OCH₃)₈] ( 2 ), and Y(Pc)[Pc(β‐OCH₃)₈] ( 3 ), as well as their reduction products {Y(Pc)[Pc(α‐OCH₃)₄]}^? ( 4 ), {Y(Pc)[Pc(α‐OCH₃)₈]}^? ( 5 ), and {Y(Pc)[Pc(β‐OCH₃)₈]}^? ( 6 ) [H₂Pc(α‐OCH₃)₄=1,8,15,22‐tetrakis(methyloxy)phthalocyanine; H₂Pc(α‐OCH₃)₈=1,4,8,11,15,18,22,25‐octakis(methyloxy)phthalocyanine; H₂Pc(β‐OCH₃)₈=2,3,9,10,16,17,23,24‐octakis(methyloxy)phthalocyanine] are studied by DFT calculations. Good consistency is found between the calculated results and experimental data for the electronic absorption, IR, and Raman spectra of 1 and 3 . Introduction of electron‐donating methyloxy groups on one phthalocyanine ring of the heteroleptic double‐deckers induces structural deformation in both phthalocyanine ligands, electron transfer between the two phthalocyanine rings, changes in orbital energy and composition, shift of electronic absorption bands, and different vibrational modes of the unsubstituted and substituted phthalocyanine ligands in the IR and Raman spectra in comparison with the unsubstituted homoleptic counterpart Y(Pc)₂. The calculations reveal that incorporation of methyloxy substituents at the nonperipheral positions has greater influence on the structure and spectroscopic properties of bis(phthalocyaninato) yttrium double‐deckers than at the peripheral positions, which increases with increasing number of substituents. Nevertheless, the substituent effect of alkyloxy substituents at one phthalocyanine ligand of the double‐decker on the unsubstituted phthalocyanine ring and on the whole molecule and the importance of the position and number of alkyloxy substituents are discussed. In addition, the effect of reducing 1 – 3 to 4 – 6 on the structure and spectroscopic properties of the bis(phthalocyaninato) yttrium compounds is also discussed. This systemic DFT study is not only useful for understanding the structure and spectroscopic properties of bis(phthalocyaninato) rare earth metal complexes but also helpful in designing and preparing double‐deckers with tunable structure and properties.