Self-sorting molecular clips

We report the synthesis and characterization of 12 C-shaped methylene-bridged glycoluril dimers (1-12) bearing H-bonding groups on their aromatic rings. Compounds 1, 2, (+/-)-4a, (+/-)-5, (+/-)-7, and 8 form tightly associated homodimers in CDCl3, due to the combined driving force of pi-pi and H-bonding interactions. Compounds 2, (+/-)-5, and 8, having disparate spatial distribution of their H-bonding groups, display the ability to efficiently distinguish between self and nonself even within three-component mixtures in CDCl3. When the spatial distributions of the H-bonding groups of the molecular clips are similar (e.g., 1 and 2), a mixture of homodimers and heterodimers is formed. The effect of various structural modifications (e.g., chirality, side chain steric bulk, number and pattern of H-bonds) on the strength of self-assembly and the fidelity of self-sorting are presented. On the basis of these results we prepared self-sorting systems comprising three (e.g., 1, (+/-)-5, and (+/-)-7) and even four ( 2, (+/-)-5, 9, and 10) components. The potential of molecular clips 1-12 as robust, functionalizable, self-sorting modules to control the noncovalent interaction network in systems chemistry studies is described.     

二元组装体集群时的高选择性杂化重组行为

多样性自组装体在混合时,通常表现出互不干扰的自分类性,能高度选择性地自分类堆积.但结构极为相似的组装子在相互混合时,会发生交互作用并表现出重组现象.文中合成和观测了具有芳香环边墙和不同酰胺侧链的C型甘脲分子夹为组装单元的混合组装行为.研究发现,此类分子在各自以单一态物质溶解于CDCl3时,能通过π-π相互作用和氢键形成二聚自组装体;若将两种具有不同酰胺侧链的C型甘脲分子夹两两混合,从理论上推测应有三种二聚自组装堆积态存在：A·A、B·B、A·B.但经1HNMR分析发现了一个有趣的现象,即当酰胺侧链上的取代基R′分别为具有C-H结构（如1和2）与PhF5基（5）的组装体两两混合时,二聚组装主要呈现出高度选择性杂化重组的A·B结构态.这种取代基控制的高选择性重组行为可能是基于π-π相互作用、N—H…O氢键,以及C—H…π等三重作用力的协同结果.     

Self-sorting: the exception or the rule?

In this paper, we pose the question of whether self-sorting in designed systems is exceptional behavior or whether it is likely to become a more general phenomenon governing molecular recognition and self-assembly. To address this question we prepared a mixture comprising two of Davis' self-assembled ionophores, Rebek's tennis ball and calixarene tetraurea capsule, Meijer's ureidopyrimidinone, Reinhoudt's calixarene bis(rosette), and two molecular clips in CDCl(3) solution and observed the behavior of this ensemble by (1)H NMR. As hypothesized, high-fidelity self-sorting behavior was observed. The influence of several key variables-temperature, concentration, equilibrium constants, and the presence of competitors-on the fidelity of self-sorting is described. These results show that self-sorting is neither the exception nor the rule. They suggest, however, that the subset of known molecular aggregates that exceed the criteria required for thermodynamic self-sorting is larger than previously appreciated and potentially quite broad.     

Controllable fabrication of a supramolecular polymer incorporating twisted cucurbit[14]uril and cucurbit[8]uril via self-sorting

A linear supramolecular polymer with controllable features based on twisted cucurbit[14]uril (tQ[14]) and cucurbit[8]uril (Q[8]) was firstly fabricated via an effective self-sorting strategy. Herein we designed a monomer, 1?butyl?1′-(naphthalen- 2-ylmethyl)-4,4′-bipyridinium bromide (BNB), that contains bipyridyl, aliphatic butyl and aromatic naphthyl groups, simultaneously. Two host molecules, tQ[14] and Q[8] were employed to develop an effective strategy for constructing a linear supramolecular polymer with controllable features. The alkyl groups on both sides of BNB could insert into the two cavities of tQ[14], the naphthyl part of BNB via π-π stacking in Q[8] cavity, serving as the driving force for supramolecular polymerization. Through self-sorting of the monomer, tQ[14] and Q[8], led to the formation of the linear supramolecular polymer. Depolymerization could be achieved by addition of adamantane hydrochloride (AH) which driven two BNB guest molecules out of the Q[8] cavity. This self-sorting strategy has great potential, not only for designing supramolecular polymer materials with different controllable structures through introduction of multiple functional groups, but also for broadening the application of twisted cucurbit[14]uril in supramolecular chemistry.     

Social self-sorting in aqueous solution

Self-sorting-the ability to efficiently distinguish between self and nonself-is common in nature but is still relatively rare in synthetic supramolecular systems. We report a 12-component mixture comprising 1-11 and KCl that undergoes thermodynamically controlled self-sorting in aqueous solution based on metal-ligand, ion-dipole, electrostatic, charge-transfer interactions, as well as the hydrophobic effect. We refer to this molecular ensemble-characterized by high-fidelity host-guest interactions between components-as a social self-sorting system to distinguish it from narcissistic self-sorting systems based on self-association processes. The influence of several key variables-temperature, pH, concentration, and host/guest stoichiometry-was explored by a combination of simulation and experiment. Variable temperature NMR experiments, for example, revealed a kinetically controlled irreversible process upon cycling from 298 to 338 K, which is an emergent property of this molecular ensemble. Variable pH and concentration experiments, in contrast, did not reveal any emergent properties of the molecular ensemble. Simulations of a four-component mixture establish that by proper control of the relative magnitude of the various equilibrium constants, it is possible to prepare socially self-sorted mixtures that are responsive (irresponsive) to host/guest stoichiometry over narrow (broad) ranges. The 12-component mixture is relatively irresponsive to host/guest stoichiometry. Such social self-sorting systems, like their natural counterparts, have potential applications as chemical sensors, as artificial regulatory elements, and in the preparation of biomimetic systems.     

Di- and tetra-nuclear copper(II), nickel(II), and cobalt(II) complexes of four bis-tetradentate triazole-based ligands: synthesis, structure, and magnetic properties

Four bis-tetradentate N(4)-substituted-3,5-{bis[bis-N-(2-pyridinemethyl)]aminomethyl}-4H-1,2,4-triazole ligands, L(Tz1)-L(Tz4), differing only in the triazole N(4) substituent R (where R is amino, pyrrolyl, phenyl, or 4-tertbutylphenyl, respectively) have been synthesized, characterized, and reacted with M(II)(BF(4))(2)·6H(2)O (M(II) = Cu, Ni or Co) and Co(SCN)(2). Experiments using all 16 possible combinations of metal salt and L(TzR) were carried out: 14 pure complexes were obtained, 11 of which are dinuclear, while the other three are tetranuclear. The dinuclear complexes include two copper(II) complexes, [Cu(II)(2)(L(Tz2))(H(2)O)(4)](BF(4))(4) (2), [Cu(II)(2)(L(Tz4))(BF(4))(2)](BF(4))(2) (4); two nickel(II) complexes, [Ni(II)(2)(L(Tz1))(H(2)O)(3)(CH(3)CN)](BF(4))(4)·0.5(CH(3)CN) (5) and [Ni(II)(2)(L(Tz4))(H(2)O)(4)](BF(4))(4)·H(2)O (8); and seven cobalt(II) complexes, [Co(II)(2)(L(Tz1))(μ-BF(4))](BF(4))(3)·H(2)O (9), [Co(II)(2)(L(Tz2))(μ-BF(4))](BF(4))(3)·2H(2)O (10), [Co(II)(2)(L(Tz3))(H(2)O)(2)](BF(4))(4) (11), [Co(II)(2)(L(Tz4))(μ-BF(4))](BF(4))(3)·3H(2)O (12), [Co(II)(2)(L(Tz1))(SCN)(4)]·3H(2)O (13), [Co(II)(2)(L(Tz2))(SCN)(4)]·2H(2)O (14), and [Co(II)(2)(L(Tz3))(SCN)(4)]·H(2)O (15). The tetranuclear complexes are [Cu(II)(4)(L(Tz1))(2)(H(2)O)(2)(BF(4))(2)](BF(4))(6) (1), [Cu(II)(4)(L(Tz3))(2)(H(2)O)(2)(μ-F)(2)](BF(4))(6)·0.5H(2)O (3), and [Ni(II)(4)(L(Tz3))(2)(H(2)O)(4)(μ-F(2))](BF(4))(6)·6.5H(2)O (7). Single crystal X-ray structure determinations revealed different solvent content from that found by microanalysis of the bulk sample after drying under a vacuum and confirmed that 5', 8', 9', 11', 12', and 15' are dinuclear while 1' and 7' are tetranuclear. As expected, magnetic measurements showed that weak antiferromagnetic intracomplex interactions are present in 1, 2, 4, 7, and 8, stabilizing a singlet spin ground state. All seven of the dinuclear cobalt(II) complexes, 9-15, have similar magnetic behavior and remain in the [HS-HS] state between 300 and 1.8 K.     

Syntheses and Crystal Structures of Cobalt(II) Chloride Complexes of 1,3-Bis(pyridyl-4-ylthio)propan-2-one

1 INTRODUCTION Widespread interest of metal-organic coordination compounds has been stirred by their intriguing struc- tural topologies and promising properties[1]. Al- though structural motifs of coordination compounds are mainly defined by metal ions’ coordination pre- ferences and chemical structures of organic ligands including the molecular angle, length and relative orientation of the donor groups[2], numerous other factors such as solvent systems, concentration, coun- terions and e…     

How does the synthesis temperature impact hybrid organic-inorganic molybdate material design?

We investigate the reactivity of MoO(4)(2-) toward six organoammonium cations (+)(Me(3-x)H(x)N)(CH(2))(2)(NH(y)Me(3-y))(+) (x, y = 1-3) at different synthesis temperatures ranging from 70 to 180 °C. A total of 16 hybrid organic-inorganic materials have been synthesized at an initial pH of 2, via ambient pressure and hydrothermal routes, namely, (H(2)en)[Mo(3)O(10)]·H(2)O (1), (H(2)en)[Mo(3)O(10)] (2), (H(2)en)[Mo(5)O(16)] (3), (H(2)MED)(2)[Mo(8)O(26)]·2H(2)O (4), (H(2)MED)[Mo(5)O(16)] (5), (N,N-H(2)DMED)(2)[Mo(8)O(26)]·2H(2)O (6), (N,N-H(2)DMED)(2)[Mo(8)O(26)]·2H(2)O (7), (N,N'-H(2)DMED)(2)[Mo(8)O(26)] (8), (N,N'-H(2)DMED)[Mo(5)O(16)] (9), (H(2)TriMED)(2)[Mo(8)O(26)]·4H(2)O (10), (H(2)TriMED)(2)[Mo(8)O(26)]·2H(2)O (11), (H(2)TriMED)[Mo(7)O(22)] (12), (H(2)TMED)(2)[Mo(8)O(26)]·2H(2)O (13), (H(2)TMED)(2)[Mo(8)O(26)] (14), (H(2)TMED)(2)[Mo(8)O(26)] (15), and (H(2)TMED)[Mo(7)O(22)] (16). All of these compounds contain different polyoxomolybdate (Mo-POM) blocks, i.e., discrete β-[Mo(8)O(26)](4-) blocks in 6, 10, 13, 14, (1)/(∞)[Mo(3)O(10)](2-), and (1)/(∞)[Mo(8)O(26)](4-) polymeric chains in 1, 2, 4, 7, 8, and 15, respectively, and (2)/(∞)[Mo(5)O(16)](2-) and (2)/(∞)[Mo(7)O(22)](2-) layers in 3, 5, 9, 12, and 16, respectively. The structures of 5, 9, and 14 have been resolved by single-crystal X-ray analyses. The characterization of the different Mo-POM blocks in 1-16 by Fourier transform Raman spectroscopy is reported. The impact of the synthesis temperature on both the composition and topology of the Mo-POM blocks is highlighted.     

Two novel Dy8 and Dy11 clusters with cubane [Dy4(μ3-OH)4]8+ units exhibiting slow magnetic relaxation behaviour

Two unique octa- and hendeca-nuclear dysprosium(III) clusters incorporating [Dy(4)(μ(3)-OH)(4)](8+) cubane units have been synthesized with the 1,10-phenanthroline-2,9-dicarbaldehyde dioxime (H(2)phendox) ligand and DyCl(3)·6H(2)O or Dy(OAc)(3)·4H(2)O. They are [Dy(8)(OH)(8)(phendox)(6)(H(2)O)(8)]Cl(2)(OH)(2)·18H(2)O·18MeOH (1) and [Dy(11)(OH)(11)(phendox)(6)(phenda)(3)(OAc)(3)](OH)·40H(2)O·7MeOH (2). Adjacent Dy(8) in 1 or Dy(11) in 2 motifs are packed by off-set π-π interactions of the aromatic rings on phendox(2-) to generate a 3D supramolecular architecture in the honeycomb topology and with 1D or 3D channels along the c-axis. Adsorption research shows that complex 1 has selective adsorption ability for H(2)O over small gas molecules (H(2), N(2), CO(2)). Complex 2 is stable upon the removal of guest molecules and the desolvated compound absorbed a considerable amount of CO(2). Furthermore, the oximes underwent hydrolysis to carboxylic acid and the resulting 1,10-phenanthroline-2,9-dicarboxylate link the dysprosium atoms to form a hendecanuclear cluster of 2. Magnetic studies reveal that both clusters exhibit slow magnetic relaxation behavior, expanding upon the recent reports of the pure 4f type single-molecule magnets (SMMs).     

Syntheses and Crystal Structures of Two Cyano-bridged Bimetallic Complexes [Ce(DMSO)4(H2O)3Fe(CN)6]·H2O and [La(DMSO)4(H2O)3Co(CN)6]·H2O (DMSO = Dimethylsulfoxide)

Two new bimetallic cyano-bridged complexes [Ce(DMSO)4(H2O)3Fe(CN)6]·H2O 1 and [La(DMSO)4(H2O)3Co(CN)6]·H2O 2 have been prepared by the ball milling reaction method and structurally characterized by X-ray single-crystal structure analyses. Crystallographic data for 1:C14H32CeFeN6O8S4, Mr = 736.67, monoclinic, space group P21/n, a = 14.952(1), b =13.7276(9), c = 15.392(1) (A), β = 108.288(1)°, V = 2999.6(4) (A)3, Z = 4, Dc= 1.631 g/cm3,μ =2.304 mm-1, F(000) = 1480, R = 0.0593 and wR = 0.1611; and those for 2: C14H32CoLaN6O8S4,Mr=738.54, monoclinic, space group P21/n, a = 14.945(3), b = 13.731(3), c = 15.300(3) (A), β=107.806(1)°, V= 2989.3(11) (A)3, Z = 4, Dc = 1.641 g/cm3,μ = 2.288 mm-1, F(000) = 1480, R =0.0383 and wR = 0.1132. In both complexes the lanthanide ion is eight-coordinated in a square antiprism arrangement, and the Fe(Ⅲ) or Co(Ⅲ) ion in a nearly regular octahedral environment.The [LnM(CN)6(DMSO)4(H2O)3]·H2O (Ln = Ce and M = Fe for 1; Ln = La and M = Co for 2)species are held together via hydrogen bonds by coordinated water molecules, lattice water molecules and nitrogen atoms of cyanide groups to form a three-dimensional framework.     

Synthesis, Structure and Topological Analysis of a New Zinc（Ⅱ） Complex [Zn2（bptc）（bpe）（H2O）]n

A novel zinc coordination polymer,[Zn 2 (bptc)(bpe)(H 2 O)] n (1,H 4 bptc=3,3,4,4-benzophenonetetracarboxylate,bpe=1,2-bis(4-pyridyl) ethane),has been prepared under hydrother-mal conditions.The crystal structure is of monoclinic,space group C/2c with a=27.50(2),b=6.207(4),c=16.233(11),β=107.522(14)°,V=2642 (3)3,C 29 H 22 N 2 O 11 Zn 2,M r=705.27,Z=4,D c=1.773 g/cm 3,F(000)=1432,μ=1.887 mm-1,R=0.0421 and wR=0.1049 for 2594 observed reflections (I > 2σ(I)).X-ray single-crystal diffraction analysis shows that 1 features two-dimensional [Zn 2 (bptc)(H 2 O)] layers,which are further linked by the bpe ligands to give rise to a three-dimensional pillar-layered structure.According to the topology analysis,this framework can be simplified into a (4,6)-connected (4 4 ·6 2)(4 4 ·6 10 ·8) network.     

Main-chain boron-containing oligophenylenes via ring-opening polymerization of 9-H-9-borafluorene

9-H-9-Borafluorene (H(8)C(12)BH; 5) can be generated in situ from 9-Br-9-borafluorene and Et(3)SiH in benzene or hexane. Monitoring of the reaction by NMR spectroscopy at rt in C(6)D(6) reveals that 5 forms C(1)-symmetric dimers (5)(2) under these conditions. DFT calculations on conceivable isomers of (5)(2) and a comparison of calculated and experimentally determined (1)H, (13)C, and (11)B NMR shift values lead to the conclusion that (5)(2) is not a classical dimer H(8)C(12)B(μ-H)(2)BC(12)H(8), but contains one B-H-B three-center, two-electron bond together with a boron-bridging phenyl ring. Addition of 1 equiv of pyridine to (5)(2) leads to the clean formation of the pyridine adduct H(8)C(12)BH(py) (5·py). Likewise, (5)(2) can be employed in hydroboration reactions, as evidenced by its transformation with 0.5 equiv of tert-butylacetylene, which gives the hydroboration products tBuC(H)(2)C(H)(BC(12)H(8))(2) (9) and tBuC(H)C(H)BC(12)H(8) in almost quantitative yield. (5)(2) is not long-term stable in benzene solution. Addition of pyridine to aged reaction mixtures allowed the isolation of the adduct (py)H(2)B-C(6)H(4)-C(6)H(4)-(py)BC(12)H(8) (10·py(2)) of a ring-opened dimer of 5. Storage of a hexane solution of 9-Br-9-borafluorene and Et(3)SiH for 1-2 weeks at rt leads to the formation of crystals of a ring-opened pentamer H[-(H)B-(C(6)H(4))(2)-](4)BC(12)H(8) (11) of 5 (preparative yields are obtained after 1-4 months). The polymer main chain of 11 is reinforced by four intrastrand B-H-B three-center, two-electron bonds. Apart from the main product 11, we have also isolated minor amounts of closely related oligomers carrying different chain ends, i.e., H(8)C(12)B-(C(6)H(4))(2)[-(H)B-(C(6)H(4))(2)-](2)BC(12)H(8) (12) and H[-(H)B-(C(6)H(4))(2)-](5)BH(2) (13). When the reaction between 9-Br-9-borafluorene and Et(3)SiH is carried out in refluxing toluene, the cyclic dimer [-(μ-H)B-(C(6)H(4))(2)-](2) (14) can be obtained in a crystalline yield of 25%. The compounds 9, 10·py(2), 11, 12, 13, and 14 have been structurally characterized by X-ray crystallography. The entire reaction pathway leading from 5 to 10, 11, 12, 13, and 14 has been thoroughly elucidated by DFT calculations and we propose a general mechanistic scenario applicable for ring-opening polymerization reactions of 9-borafluorenes.     

Integrative self-sorting: construction of a cascade-stoppered hetero[3]rotaxane

In this Communication, a competing self-sorting system containing benzo-21-crown-7, dibenzo-24-crown-8 and two secondary ammonium salts is constructed, which is then modified to achieve a hetero[3]pseudorotaxane with a specific sequence of wheels. With these two systems, we successfully demonstrate the concept of integrative self-sorting, and their relation. Furthermore, based on this self-sorting scheme, a hetero[3]rotaxane with an efficient stopper cascade has been synthesized.     

Formation of a N2-dG:N2-dG carbinolamine DNA cross-link by the trans-4-hydroxynonenal-derived (6S,8R,11S) 1,N2-dG adduct

Michael addition of trans-4-hydroxynonenal (HNE) to deoxyguanosine yields diastereomeric 1,N(2)-dG adducts in DNA. When placed opposite dC in the 5'-CpG-3' sequence, the (6S,8R,11S) diastereomer forms a N(2)-dG:N(2)-dG interstrand cross-link [Wang, H.; Kozekov, I. D.; Harris, T. M.; Rizzo, C. J. J. Am. Chem. Soc.2003, 125, 5687-5700]. We refined its structure in 5'-d(G(1)C(2)T(3)A(4)G(5)C(6)X(7)A(8)G(9)T(10)C(11)C(12))-3'·5'-d(G(13)G(14)A(15)C(16)T(17)C(18)Y(19)C(20)T(21)A(22)G(23)C(24))-3' [X(7) is the dG adjacent to the C6 carbon of the cross-link or the α-carbon of the (6S,8R,11S) 1,N(2)-dG adduct, and Y(19) is the dG adjacent to the C8 carbon of the cross-link or the γ-carbon of the HNE-derived (6S,8R,11S) 1,N(2)-dG adduct; the cross-link is in the 5'-CpG-3' sequence]. Introduction of (13)C at the C8 carbon of the cross-link revealed one (13)C8→H8 correlation, indicating that the cross-link existed predominantly as a carbinolamine linkage. The H8 proton exhibited NOEs to Y(19) H1', C(20) H1', and C(20) H4', orienting it toward the complementary strand, consistent with the (6S,8R,11S) configuration. An NOE was also observed between the HNE H11 proton and Y(19) H1', orienting the former toward the complementary strand. Imine and pyrimidopurinone linkages were excluded by observation of the Y(19)N(2)H and X(7) N1H protons, respectively. A strong H8→H11 NOE and no (3)J((13)C→H) coupling for the (13)C8-O-C11-H11 eliminated the tetrahydrofuran species derived from the (6S,8R,11S) 1,N(2)-dG adduct. The (6S,8R,11S) carbinolamine linkage and the HNE side chain were located in the minor groove. The X(7)N(2) and Y(19)N(2) atoms were in the gauche conformation with respect to the linkage, maintaining Watson-Crick hydrogen bonds at the cross-linked base pairs. A solvated molecular dynamics simulation indicated that the anti conformation of the hydroxyl group with respect to C6 of the tether minimized steric interaction and predicted hydrogen bonds involving O8H with C(20)O(2) of the 5'-neighbor base pair G(5)·C(20) and O11H with C(18)O(2) of X(7)·C(18). These may, in part, explain the stability of this cross-link and the stereochemical preference for the (6S,8R,11S) configuration.     

Investigation of Intermolecular C-H···Halogen Hydrogen Bonded Supramolecular Assemblies in Three Copper(Ⅰ) Complexes Formed by 3,3'-Dimethoxy-6,6'-dimethyl-2,2'-bipyridine Ligand

Three new crystalline compounds 1-3 were successfully obtained by the reactions of 3,3'-dimethoxy-6,6'-dimethyl-2,2'-bipyridine ligand(dmbp) with the corresponding Cu(Ⅰ) salts.Crystal data for 1:orthorhombic Pbca,a = 18.5858(12),b = 8.1821(5),c = 20.6066(13) ,V = 3133.7(3) 3,Z = 8,Dc = 1.843 g/cm3,F(000) = 1696,μ = 3.366 mm-1,the final R = 0.0223 and wR = 0.0542.Crystal data for 2:Orthorhombic Pbca,a = 18.7883(16),b = 8.3249(7),c = 19.0294(17) ,V = 2976.4(4) 3,Z = 8,Dc = 1.731 g/cm3,F(000) = 1552,μ = 4.154 mm-1,the final R = 0.0279 and wR = 0.0680.Crystal data for 3:monoclinic P21/c,a = 13.812(10),b = 9.910(7),c = 23.444(17) ,β = 104.3350(10)°,V = 3090(4) 3,Z = 4,Dc = 1.476 g/cm3,F(000) = 1408,μ = 1.588 mm-1,the final R = 0.0479 and wR = 0.1081.The results of X-ray crystallographic analysis revealed that C14H16ICuN2O2(1) and C14H16BrCuN2O2(2) are isostructural compounds with the dimers connected by C-H···halogen hydrogen bonds to generate a three-dimensional(3D) supramolecular network in 1 and a two-dimensional(2D) sheet structure in 2,respectively,while the mononuclear complex C28H32Cl2Cu2N4O4(3) is ionic.In 3,the [Cu(dmbp)2]+ cations and [ClCuCl]-anions are connected by C-H···Cl hydrogen bonds to form a one-dimensional(1D) chain along the a axis.Therefore,in the three complexes,the C-H···halogen hydrogen bonds dominate their crystal structures.Additionally,The UV luminescent properties of complexes 1-3 were investigated.     

Enantioselective resolutions and circular dichroism studies of lanthanide-containing Keggin-type [Ln(PW11O39)2](11-) polyoxometalates

Enantiopure crystals of K(1.3)Na(3.2)H(6.5)[l-Pr(PW(11)O(39))(2)]·8.3l-proline·21.5H(2)O (1), K(1.3)Na(3.2)H(6.5)[d-Pr(PW(11)O(39))(2)]·8.3d-proline·17H(2)O (2), and K(1.3)Na(3.2)H(6.5)[l-Er(PW(11)O(39))(2)]·8.3l-proline·22.5H(2)O (3) were successfully obtained by using l- and d-proline (pro) as chiral auxiliary agents. In these crystals, l- and d-[Ln(PW(11)O(39))(2)](11-) anions are attached by two l- and d-pro molecules, respectively, through a O···N hydrogen-bonding interaction between the square-antiprismatic LnO(8) center and amino-N atoms. The l- and d-[Pr(PW(11)O(39))(2)](11-) anions in aqueous solutions exhibited a couple of mirror-imaged CD spectra due to (3)H(4/2)→(3)P(0,1,2) and (1)D(2) transitions in the stereogenic Pr(3+) center. Chirality inductions by l- and d-pro from a racemic solution of [Er(PW(11)O(39))(2)](11-) was demonstrated by means of CD spectroscopy.     

一个基于偶氮六酸的稀土金属-有机框架

采用1,2,3-三羧基-(1′,2′,3′-三羧基偶氮苯)-苯(H₆TTAB)连接线性四核铕配位单元, 组装形成具有 {4¹⁴·6²⁰·8¹¹}{4³}₂{4⁵·6}拓扑结构的稀土金属-有机框架Eu-TTAB. Eu-TTAB具有高的热和溶剂稳定性, 在紫外光激发下具有发光性质, 且其发光性能可以被铽离子调控并被银离子大幅度提升.     

Extended polyoxometalate framework solids: two Mn(II)-linked {P8W48} network arrays

Two polyoxometalate open framework (POMOF) materials have been synthesized using a secondary building unit (SBU) approach that facilitates the convergent assembly of multidimensional framework materials using a preassembled anionic SBU {P(8)W(48)}, with integrated "pore" 1 nm in diameter, and electrophilic manganese {Mn(2+)} linkers. This yields two new POMOFS with augmented hexagonal tiling (2 and 3), related to a known three-dimensional (3D) cubic array K(18)Li(6)[Mn(II)(8)(H(2)O)(48)P(8)W(48)O(184)]·108H(2)O (1), K(12)[Mn(II)(14)(H(2)O)(30)P(8)W(48)O(184)]·111H(2)O (2), and K(8)Li(4)[Mn(II)(14)(H(2)O)(26)P(8)W(48)O(184)]·105H(2)O (3). These frameworks have been crystallized from aqueous Li-buffered solutions of {P(8)W(48)} and Mn(II)(ClO(4))(2)·6H(2)O via careful control of the synthetic strategy akin to a crystal engineering approach using cation and temperature control to isolate different material architectures shown by compounds 1-3.     

Synthesis and Structure of { (Tab-Tab) [Ag2(μ-Cl)4]·2MeCN}n (Tab = 4-(Trimethylammonio)benzenethiolate)

In the presence of Et4NCl?H2O,reaction of AgCl with TabHPF6 in MeCN afforded the title complex {(Tab-Tab)[Ag2(μ-Cl)4]·2MeCN}n 1.1 crystallizes in the orthorhombic space group Pbcn with a=16.782(3),b=6.8358(14),c=26.194(5) ,V=3004.9(10) 3,Z=8,μ= 1.817 mm-1,Dc=1.711 g/cm3,T=223 K,C11H16AgCl2N2S,Mr=387.10,F(000)=1544,S=1.160,R=0.0528 and wR=0.0896 for 2732 observed reflections with I > 2σ(I).1 contains a 1D linear [Ag2Cl4]n2n-chain coupled with the [Tab-Tab]2+ dications.Intermolecular hydrogen bonding interac-tions between the protons of methyl groups from the Tab-Tab dications and the chlorides result in the formation of a 2D hydrogen-bonded network.     

Synthesis and structures of cuprous triptycylthiolate complexes

A synthesis of 1-(thioacetyl)triptycene (5), a convenient protected form of 1-(thiolato)triptycene [STrip](-), is described, a key transformation being the high yield conversion of tert-butyl 1-triptycenyl sulfide (8) to 5 by a protocol employing BBr(3)/AcCl. Syntheses of the two-coordinate copper(I) compounds [Bu(4)N][Cu(STrip)(2)], [Bu(4)N]10, and [(Cu(IMes)(STrip)] (13) proceed readily by chloride displacement from CuCl and [Cu(IMes)Cl], respectively. Reaction of 10 with Ph(3)SiSH or Me(3)SiI produces the heteroleptic species [Cu(STrip)(SSiPh(3))](-) (11) and [Cu(STrip)I](-) (12), detected by mass spectrometry, in mixture with the homoleptic bis(thiolate) anions. Structural identification by X-ray crystallography of the ligand precursor molecules 9-(thioacetyl)anthracene (4, triclinic and orthorhombic polymorphs), tert-butyl 9-anthracenyl sulfide (7), 5, and tert-butyl 1-triptycenyl sulfide (8) are presented. Crystallographic characterization of bis(9-anthracenyl)sulfide (3), which features a C-S-C angle of 104.0° and twist angle of 54.8° between anthracenyl planes, is also given. A crystal structure of [Bu(4)N][(STrip)], [Bu(4)N]9, provides an experimental measure of 144.6° for the ligand cone angle. The crystal structures of [Bu(4)N]10 and 13 are reported, the former of which reveals an unexpectedly small C-S···S-C torsion angle of ～41° (average of two values), which confers a near "cis" disposition of the triptycenyl groups with respect the S-Cu-S axis. This conformation is governed by interligand π···π and CH···π interactions. A crystal structure of an adventitious product, [Bu(4)N][(Cu-STrip)(6)(μ(6)-Br)]·[Bu(4)N][PF(6)], [Bu(4)N]14·[Bu(4)N][PF(6)] is described, which reveals a cyclic hexameric structure previously unobserved in cuprous thiolate chemistry. The Cu(6)S(6) ring displays a centrosymmetric cyclohexane chair type conformation with a Br(-) ion residing at the inversion center and held in place by apparent soft-soft interactions with the Cu(I) ions.