Supramolecular strategy for smart windows.

Smart windows are a promising solution to improve energy-saving efficiency and indoor comfort due to their potential functionalities including solar modulation, coloration, self-cleaning, self-power, and moisture scavenging. Recently, smart windows constructed by a supramolecular strategy have attracted increasing attention due to the inherent dynamic, reversible and adaptive properties of noncovalent interactions, which can endow the fabricated smart windows with desired fascinating functionalities. In this review, emerging supramolecular strategy-based materials are outlined and their applications for fabricating smart windows are summarized. Mechanisms and properties of the functional supramolecular materials are demonstrated, especially their solar modulation ability and color change effect. Challenges and opportunities for the supramolecular strategy-based materials are also discussed for future innovation in the development of ideal smart windows.

Warm/cool-tone switchable thermochromic material for smart windows by orthogonally integrating properties of pillar[6]arene and ferrocene.

Functional materials play a vital role in the fabrication of smart windows, which can provide a more comfortable indoor environment for humans to enjoy a better lifestyle. Traditional materials for smart windows tend to possess only a single functionality with the purpose of regulating the input of solar energy. However, different color tones also have great influences on human emotions. Herein, a strategy for orthogonal integration of different properties is proposed, namely the thermo-responsiveness of ethylene glycol-modified pillar[6]arene (EGP6) and the redox-induced reversible color switching of ferrocene/ferrocenium groups are orthogonally integrated into one system. This gives rise to a material with cooperative and non-interfering dual functions, featuring both thermochromism and warm/cool tone-switchability. Consequently, the obtained bifunctional material for fabricating smart windows can not only regulate the input of solar energy but also can provide a more comfortable color tone to improve the feelings and emotions of people in indoor environments.

Multistimuli-responsive supramolecular vesicles based on water-soluble pillar[6]arene and SAINT complexation for controllable drug release.

Supramolecular binary vesicles based on the host-guest complexation of water-soluble pillar[6]arene (WP6) and SAINT molecule have been successfully constructed, which showed pH-, Ca(2+)-, and thermal-responsiveness. These supramolecular vesicles can efficiently encapsulate model substrate calcein, which then can be efficiently released either by adjusting the solution pH to acidic condition due to the complete disruption of vesicular structure, or particularly, by adding a certain amount of Ca(2+) due to the Ca(2+)-induced vesicle fusion and accompanied by the structure disruption. More importantly, drug loading and releasing experiments demonstrate that an anticancer drug, DOX, can be successfully encapsulated by the supramolecular vesicles, and the resulting DOX-loaded vesicles exhibit efficient release of the encapsulated DOX with the pH adjustment or the introduction of Ca(2+). Cytotoxicity experiments suggest that the resulting DOX-loaded supramolecular vesicles exhibit comparable therapeutic effect for cancer cells as free DOX and the remarkably reduced damage for normal cells as well. The present multistimuli-responsive supramolecular vesicles have great potential applications in the field of controlled drug delivery. In addition, giant supramolecular vesicles (~3 µm) with large internal volume and good stability can be achieved by increasing the temperature of WP6 ⊃ SAINT vesicular solution, and they might have potential applications for bioimaging.

Two lanthanum(III) complexes containing η2-pyrazolate and η2-1,2,4-triazolate ligands: intramolecular C-H...N/O interactions and coordination geometries.

The lanthanum(III) complexes tris(3,5-diphenylpyrazolato-κ(2)N,N')tris(tetrahydrofuran-κO)lanthanum(III) tetrahydrofuran monosolvate, [La(C(15)H(11)N(2))(3)(C(4)H(8)O)(3)]·C(4)H(8)O, (I), and tris(3,5-diphenyl-1,2,4-triazolato-κ(2)N(1),N(2))tris(tetrahydrofuran-κO)lanthanum(III), [La(C(14)H(10)N(3))(3)(C(4)H(8)O)(3)], (II), both contain La(III) atoms coordinated by three heterocyclic ligands and three tetrahydrofuran ligands, but their coordination geometries differ. Complex (I) has a mer-distorted octahedral geometry, while complex (II) has a fac-distorted configuration. The difference in the coordination geometries and the existence of asymmetric La-N bonding in the two complexes is associated with intramolecular C-H...N/O interactions between the ligands.

Bis[µ-N,N'-bis(quinolin-8-yl)pyridine-2,6-dicarboxamido]dizinc(II) dichloromethane disolvate.

The title compound, [Zn(2)(C(25)H(15)N(5)O(2))(2)]·2CH(2)Cl(2), is a dinuclear double-helical complex which lies on a crystallographic twofold axis. In the complex, both ligands are partitioned into two tridentate domains which allow each ligand to bridge both metal centres. Each Zn(II) atom is six-coordinated in a distorted octahedral environment formed by two amide N atoms, two quinoline N atoms and two pyridine N atoms from two different ligand molecules, with the central pyridine ring, unusually, bridging two Zn(II) atoms. The deprotonated ligand is not planar, the amide side chains being considerably twisted out from the plane of the central pyridine ring.

Unprecedented NaI-CuII-LnIII heterometallic coordination polymers based on 3,5-pyrazoledicarboxylate with both infinite cationic and anionic chains.

The self-assembly of 3,5-pyrazoledicarboxylic acid (H3pdc) and metal salts under hydrothermal conditions leads to the formation of a series of novel NaI-CuII-LnIII heterometallic coordination polymers, [[Na(H2O)4]2[Cu(pdc)2Ln(H2O)5]2 x 3H2O]n [Ln = La (1); Sm (2); Pr (3); Nd (4) and pdc3- = 3,5-pyrazoledicarboxylate]. X-Ray structure analyses show that these complexes all exhibit pairs of infinite, unexpected, cationic and anionic chains. It is the first successful attempt to construct unprecedented NaI-CuII-LnIII heterometallic coordination polymers with both infinite cationic and anionic chains. These four complexes show homologous thermal stabilities. The different magnetic properties of are also been reported in this paper.

A novel three-dimensional heterometalliccoordination polymer:poly[[hexaaquabis[mu3-3,5-dicarboxylatopyrazolato-kappa5O3,N2:N1,O5:O50]-(mu2-oxalato-kappa4O1,O2:O10,O20)-copper(II)dierbium(III)] trihydrate].

The title novel heterometallic 3d-4f coordination polymer, {[CuEr(2)(C(5)HN(2)O(4))(2)(C(2)O(4))(H(2)O)(6)].3H(2)O}(n), has a three-dimensional metal-organic framework composed of two types of metal atoms (one Cu(II) and two Er(III)) and two types of bridging anionic ligands [3,5-dicarboxylatopyrazolate(3-) (ptc(3-)) and oxalate]. The Cu(II) atom is four-coordinated in a square geometry. The Er(III) atoms are both eight-coordinated, but the geometries at the two atoms appear different, viz. triangular dodecahedral and bicapped trigonal prismatic. One of the oxalate anions is located on a twofold axis and the other lies about an inversion centre. Both oxalate anions act as bis-bidentate ligands bridging the latter type of Er atoms in parallel zigzag chains. The pdc(3-) anions act as quinquedentate ligands not only chelating the Cu(II) and the triangular dodecahedral Er(III) centres in a bis-bidentate bridging mode, but also connecting to Er(III) centres of both types in a monodentate bridging mode. Thus, a three-dimensional metal-organic framework is generated, and hydrogen bonds link the metal-organic framework with the uncoordinated water molecules. This study describes the first example of a three-dimensional 3d-4f coordination polymer based on pyrazole-3,5-dicarboxylate and oxalate, and therefore demonstrates further the usefulness of pyrazoledicarboxylate as a versatile multidentate ligand for constructing heterometallic 3d-4f coordination polymers with interesting architectures.

Poly[[tetra-aqua-(µ(6)-2,2'-diiodo-biphenyl-4,4',5,5'-tetra-carboxyl-ato)dizinc(II)] dihydrate].

In the title compound, {[Zn(2)(C(16)H(4)I(2)O(8))(H(2)O)(4)]·2H(2)O}(n), two crystallographically independent Zn(II) atoms are each located on a twofold rotation axis. Both Zn(II) atoms are in distorted octa-hedral coordination geometries: one is coordinated by six O atoms from four carboxyl-ate groups, while the other is coordinated by two carboxyl-ate groups and four water mol-ecules. The tetra-carboxyl-ate ligand mol-ecules connect the Zn(II) atoms, completing a three-dimensional metal-organic framework. O-H⋯O hydrogen bonds link the metal-organic framework with the uncoord-inated water mol-ecules.