Helical chirality of π‐conjugated main‐chain induced by polymerization of phenylacetylene with chiral bulky pinanyl groups: Effects of the flexible spacer and polymerization catalyst

Three optically active phenylacetylene polymers with chiral bulky pinanyl groups, (?)‐poly[4‐(dimethylpinanylsilyl)phenylacetylene] [(?)‐poly(PSPA)], (+)‐poly{4‐[3‐(10‐pinanyl)tetramethyldisiloxy]phenylacethylene} [(+)‐poly(PDSPA)], and their copolymer [(?)‐copoly(PSPA/PDSPA)], were synthesized. We observed high chirality in the main‐chain chromophore of (?)‐poly(PSPA), due to the presence of a chiral helix, with circular dichroism spectroscopy. In contrast, (+)‐poly(PDSPA),with flexible SiOSi spacers between the chiral pinanyl group and the main chain, had lower chirality. (?)‐Poly(PSPA), with large circular dichroism signals, was prepared by polymerization with a rhodium catalyst and had a highly stereoregular main chain (high cis‐configuration percentage). However, (?)‐poly(PSPA) prepared with a tungsten catalyst had lower chirality and lower stereoregularity in the main chain. A membrane from (?)‐poly(PSPA) showed enantioselective permeability for tryptophan in an aqueous solution. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1689–1697, 2002     

Unusual H‐Bond Topology and Bifurcated H‐bonds in the 2‐Fluoroethanol Trimer

By using a combination of rotational spectroscopy and ab initio calculations, an unusual H‐bond topology was revealed for the 2‐fluoroethanol trimer. The trimer exhibits a strong heterochiral preference and adopts an open OH???OH H‐bond topology while utilizing two types of bifurcated H‐bonds involving organic fluorine. This is in stark contrast to the cyclic OH???OH H‐bond topology adopted by trimers of water and other simple alcohols. The strengths of different H‐bonds in the trimer were analyzed by using the quantum theory of atoms in molecules. The study showcases a remarkable example of a chirality‐induced switch in H‐bond topology in a simple transient chiral fluoroalcohol. It provides important insight into the H‐bond topologies of small fluoroalcohol aggregates, which are proposed to play a key role in protein folding and in enantioselective reactions and separations where fluoroalcohols serve as a (co)solvent.     

Ultrasound-induced emission enhancement based on structure-dependent homo- and heterochiral aggregations of chiral binuclear platinum complexes

Instant and precise control of phosphorescent emission can be performed by ultrasound-induced gelation of organic liquids with chiral, clothespin-shaped trans-bis(salicylaldiminato)Pt(II) complexes, anti-1. Nonemissive solutions of racemic, short-linked anti-1a (n = 5) and optically pure, long-linked anti-1c (n = 7) in organic liquids are transformed immediately into stable phosphorescent gels upon brief irradiation of low-power ultrasound. Emission from the gels can be controlled by sonication time, linker length, and optical activity of the complexes. Several experimental results indicated that structure-dependent homo- and heterochiral aggregations and ultrasound-control of the aggregate morphology are key factors for emission enhancement.     

Synthesis of Diacetylene‐Containing Peptide Building Blocks and Amphiphiles,Their Self‐Assembly and Topochemical Polymerization in Organic Solvents

A series of functional iodoacetylenes was prepared and converted into the corresponding diacetylene‐substituted amino acids and peptides via Pd/Cu‐promoted sp–sp carbon cross‐coupling reactions. The unsymmetrically substituted diacetylenes can be incorporated into oligopeptides without a change in the oligopeptide strand's directionality. Thus, a series of oligopeptide‐based, amphiphilic diacetylene model compounds was synthesized, and their self‐organization as well as their UV‐induced topochemical polymerizability was investigated in comparison to related polymer‐substituted macromonomers. Solution‐phase IR spectroscopy, gelation experiments, and UV spectroscopy helped to confirm that a minimum of five N‐H???O?C hydrogen‐bonding sites was required in order to obtain reliable aggregation into stable β‐sheet‐type secondary structures in organic solvents. Furthermore, the non‐equidistant spacing of these hydrogen‐bonding sites was proven to invariably lead to β‐sheets with a parallel β‐strand orientation, and the characteristic IR‐spectroscopic signatures of the latter in organic solution was identified. Scanning force micrographs of the organogels revealed that compounds with six hydrogen‐bonding sites gave rise to high aspect ratio nanoscopic fibrils with helical superstructures but, in contrast to the related macromonomers, did not lead to uniform supramolecular polymers. The UV‐induced topochemical polymerization within the β‐sheet aggregates was successful, proving parallel β‐strand orientation and highlighting the effect of the number and pattern of N‐H???O?C hydrogen‐bonding sites as well as the hydrophobic residue in the molecular structure on the formation of higher structures and reactivity.     

Spontaneous transmission of chirality through multiple length scales

The hierarchical transfer of chirality in nature, from the nano‐, to meso‐, to macroscopic length scales, is very complex, and as of yet, not well understood. The advent of scanning probes has allowed chirality to be monitored at the single molecule or monolayer level and has opened up the possibility to track enantiospecific interactions and chiral self‐assembly with molecular‐scale detail. This paper describes the self‐assembly of a simple, model molecule (naphtho[2,3‐a]pyrene) that is achiral in the gas phase, but becomes chiral when adsorbed on a surface. This polyaromatic hydrocarbon forms a stable and reversibly ordered system on Cu(111) in which the transmission of chirality from single surface‐bound molecules to complex 2D chiral architectures can be monitored as a function of molecular packing density and surface temperature. In addition to the point chirality of the surface‐bound molecule, the unit cell of the molecular domains was also found to be chiral due to the incommensurate alignment of the molecular rows with respect to the underlying metal lattice. These molecular domains always aggregated in groups of three, all of the same chirality, but with different rotational orientations, forming homochiral “tri‐lobe” ensembles. At a larger length scale, these tri‐lobe ensembles associated with nearest‐neighbor tri‐lobe units of opposite chirality at lower packing densities before forming an extended array of homochiral tri‐lobe ensembles at higher converges. This system displayed chirality at a variety of size scales from the molecular (≈1 nm) and domain (≈5 nm) to the tri‐lobe ensemble (≈10 nm) and extended array (>25 nm) levels. The chirality of the tri‐lobe ensembles dictated how the overall surface packing occurred and both homo‐ and heterochiral arrays could be reproducibly and reversibly formed and interchanged as a function of surface coverage. Finally, these chirally templated surfaces displayed remarkable enantiospecificity for naphtho[2,3‐a]pyrene molecules adsorbed in the second layer. Given its simplicity, reversibility, and rich degree of order, this system represents an ideal test bed for the investigation of symmetry breaking and the hierarchical transmission of chirality through multiple length scales.     

Circularly Polarized Luminescence of Chiral Pt(pppb)Cl (pppbH=1‐pyridyl‐3‐(4,5‐pinenopyridyl)benzene) Aggregate in the Excited State

We prepared enantiomers of chiral Pt^II complexes, Pt(pppb)Cl and Pt(pppb)CN (pppbH=1‐pyridyl‐3‐(4,5‐pinenopyridyl)benzene), and measured their CPL (circularly polarized luminescence) spectra for excimer and trimer emission. The contribution of the pinene moiety to CPL was considerably low for the π–π* emission of the monomer but large for MMLCT (metal‐metal‐to‐ligand charge‐transfer) of the excimer and trimer which had a helical structure induced in a face‐to‐face stacking fashion. The trimer CPL for (+)‐Pt(pppb)Cl was larger in intensity than that of excimer CPL; on the other hand, that for (+)‐Pt(pppb)CN was opposite in sign compared with that of excimer CPL. We conclude that differences in the excited‐state structure of the aggregate between Pt(pppb)Cl and Pt(pppb)CN account for the variation in the CPL spectra. By the aid of TD‐DFT calculations it was predicted that the dihedral angle θ(Cl‐Pt‐Pt‐Cl) was 50–60° or 110–140° for Pt(pppb)Cl aggregates and 160° for Pt(pppb)CN aggregates.     

Water‐Binding‐Mediated Gelation/Crystallization and Thermosensitive Superchirality

Determination of molecular structural parameters of hydrophobic cholesterol–naphthalimide conjugates for water binding capabilities as well as their moisture‐sensitive supramolecular self‐assembly were revealed. Water binding was a key factor in leading trace water‐induced crystallization against gelation in apolar solvent. Ordered water molecules entrapped in self‐assembly arrays revealed by crystal structures behave as hydrogen‐bonding linkers to facilitate three‐dimensional growth into crystals rather than one‐dimensional gel nanofibers. Water binding was also reflected on the supramolecular chirality inversion of vesicle self‐assembly in aqueous media via heating‐induced dehydration. Structural parameters that favor water binding were evaluated in detail, which could help rationally design organic building units for advancing soft materials, crystal engineering, and chiral recognition.     

Chiral Reticular Self‐Assembly of Achiral AIEgen into Optically Pure Metal–Organic Frameworks (MOFs) with Dual Mechano‐Switchable Circularly Polarized Luminescence

Circularly polarized luminescence (CPL) is attractive in understanding the excited‐state chirality and developing advanced materials. Herein, we propose a chiral reticular self‐assembly strategy to unite achiral AIEgens, chirality donors, and metal ions to fabricate optically pure AIEgen metal–organic frameworks (MOFs) as efficient CPL materials. We have found that CPL activity of the single‐crystal AIEgen MOF was generated by the framework‐enabled strong emission from AIEgens and through‐space chirality transfer from chirality donors to achiral AIEgens via metal‐ion bridges. For the first time, a dual mechano‐switched blue and red‐shifted CPL activity was achieved via ultrasonication and grinding, which enabled the rotation or stacking change of AIEgen rotors with the intact homochiral framework. This work provided not only an insightful view of the aggregation induced emission (AIE) mechanism, but also an efficient and versatile strategy for the preparation of stimuli‐responsive CPL materials.     

Tuning of Supramolecular Architectures of l‐Valine‐Containing Dicyanoplatinum(II) 2,2′‐Bipyridine Complexes by Metal–Metal, π–π Stacking,and Hydrogen‐Bonding Interactions

A series of newly synthesized dicyanoplatinum(II) 2,2′‐bipyridine complexes exhibits self‐assembly properties in solution after the incorporation of the l ‐valine amino units appended with various hydrophobic motifs. These l ‐valine‐derived substituents were found to have critical control over the aggregation behaviors of the complexes in the solution state. On one hand, one of the complexes was found to exhibit interesting circularly polarized luminescence (CPL) signals at low temperature due to the formation of chiral spherical aggregates in the temperature‐dependent studies. On the other hand, systematic transformation from less uniform aggregates to well‐defined fibrous and rod‐like structures via Pt???Pt and π–π stacking interactions has also been observed in the mixed‐solvent studies. These changes were monitored by UV/Vis absorption, emission, circular dichroism (CD), and CPL spectroscopies, and morphologies were studied by electron microscopy.     

A Motif for Infinite Metal Atom Wires

A new motif for infinite metal atom wires with tunable compositions and properties is developed based on the connection between metal paddlewheel and square planar complex moieties. Two infinite Pd chain compounds, [Pd₄(CO)₄(OAc)₄Pd(acac)₂] 1 and [Pd₄(CO)₄(TFA)₄Pd(acac)₂] 2 , and an infinite Pd? Pt heterometallic chain compound, [Pd₄(CO)₄(OAc)₄Pt(acac)₂] 3 , are identified by single‐crystal X‐ray diffraction analysis. In these new structures, the paddlewheel moiety is a Pd four‐membered ring coordinated by bridging carboxylic ligands and μ₂ carbonyl ligands. The planar moiety is either Pd(acac)₂ or Pt(acac)₂ (acac=acetylacetonate). These moieties are connected by metallophilic interactions. The results showed that these one‐dimensional metal wire compounds have photoluminescent properties that are tunable by changing ligands and metal ions. 3 can also serve as a single source precursor for making Pd₄Pt bimetallic nanostructures with precise control of metal composition.     

p‐Quaterphenylene as an Aggregation‐Induced Emission Fluorogen in Supramolecular Organogels and Fluorescent Sensors

Two dumbbell‐shaped organogelators with a p ‐quaterphenylene core were synthesized, and their self‐assembly properties were investigated. These low‐molecular‐weight gelators could form self‐supporting gels in many apolar organic solvents with an H‐type aggregation form through a synergic effect of π–π stacking, intermolecular translation‐related hydrogen bonding, and van der Waals forces. In comparison to the p ‐terphenylene‐cored gelator, the extended π‐conjugated segment improved the gelation efficiency significantly with enhanced gelation rate. Additionally, these p ‐quaterphenylene‐centered gelators exhibited strong fluorescence emission induced by aggregation, which not only provided an in situ method to optically monitor the gelation process, but also endowed these self‐assemblies with substantial applications in sensing explosives.     

Non‐covalent Versus Covalent Control of Self‐Assembly and Chirality of Nile Red‐modified Nucleoside and DNA

A DNA‐based covalent versus a non‐covalent approach is demonstrated to control the optical, chirooptical and higher order structures of Nile red ( Nr ) aggregation. Dynamic light scattering and TEM studies revealed that in aqueous media Nr ‐modified 2′‐deoxyuridine aggregates through the co‐operative effect of various non‐covalent interactions including the hydrogen bonding ability of the nucleoside and sugar moieties and the π‐stacking tendency of the highly hydrophobic dye. This results in the formation of optically active nanovesicles. A left‐handed helically twisted H‐type packing of the dye is observed in the bilayer of the vesicle as evidenced from the optical and chirooptical studies. On the other hand, a left‐handed helically twisted J‐type packing in vesicles was obtained from a non‐polar solvent (toluene). Even though the primary stacking interaction of the dye aggregates transformed from H→J while going from aqueous to non‐polar media, the induced supramolecular chirality of the aggregates remained the same (left‐handed). Circular dichroism studies of DNA that contained several synthetically incorporated and covalently attached Nr ‐modified nucleosides revealed the formation of helically stacked H‐aggregates of Nr but—in comparison to the noncovalent aggregates—an inversed chirality (right‐handed). This self‐assembly propensity difference can, in principle, be applied to other hydrophobic dyes and chromophores and thus open a DNA‐based approach to modulate the primary stacking interactions and supramolecular chirality of dye aggregates.     

Synthesis and characterization of well‐defined optically active methacrylic diblock copolymers

A new, simple, and cost‐effective approach toward the development of well‐defined optically active diblock copolymers based on methacrylate monomers is described for the first time. Starting from the low‐cost optically active (S)‐(?)‐2‐methyl‐1‐butanol, a new optically active methacrylic monomer, namely, (S)‐(+)‐2‐methyl‐1‐butyl methacrylate [(S)‐(+)‐MBuMA], was synthesized. Reversible addition fragmentation chain transfer polymerization was then used for preparing well‐defined poly[(S)‐(+)‐MBuMA] homopolymers and water‐soluble diblock copolymers based on [(S)‐(+)‐MBuMA] and the hydrophilic and ionizable monomer 2‐(dimethyl amino)ethyl methacrylate (DMAEMA). The respective homopolymers and diblock copolymers were characterized in terms of their molecular weights, polydispersity indices, and compositions by size exclusion chromatography and ¹H NMR spectroscopy. Polarimetry measurements were used to determine the specific optical rotations of these systems. The structural and compositional characteristics of micellar nanostructures possessing an optically active core generated by p((S)‐(+)‐MBuMA)‐b‐p(DMAEMA) chains characterized by predetermined molecular characteristics may be easily tuned to match biological constructs. Consequently, the aggregation behavior of the p[(S)‐(+)‐MBuMA]‐b‐p[DMAEMA] diblock copolymers was investigated in aqueous media by means of dynamic light scattering and atomic force microscopy, which revealed the formation of micelles in neutral and acidified aqueous solutions. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

A Platinum(II) Terpyridine Metallogel with an L‐Valine‐Modified Alkynyl Ligand: Interplay of Pt⋅⋅⋅Pt, π–π and Hydrogen‐Bonding Interactions

A series of platinum(II) terpyridine complexes with L ‐valine‐modified alkynyl ligands has been synthesized. A complex with an unsubstituted terpyridine and one valine unit on the alkynyl is shown to be capable of gel formation, which is in sharp contrast to the gelation properties of the corresponding organic counterparts. Upon sol–gel transition, a drastic color change from yellow to red is observed, which is indicative of the involvement of Pt ??? Pt interactions. Through the concentration‐ and temperature‐dependent UV/Vis absorption, emission, circular dichroism, and ¹H NMR studies, the contribution of hydrogen bonding, Pt ??? Pt and π–π stacking interactions as driving forces for gelation have been established, and the importance of maintaining a delicate balance between different intermolecular forces has also been illustrated.     

Rational Topological Design for Fluorescence Enhancement upon Aggregation of Distyrylfuran Derivatives

A series of 2,5‐distyrylfuran derivatives bearing pentafluorophenyl‐ and cyanovinyl units have been synthesized for aggregation‐induced emission (AIE). The effect of the type and extent of the supramolecular connections on the AIE of the furan derivatives were examined and correlated with their X‐ray crystal structures. It was found that the simultaneous presence of cyano and perfluorophenyl units strongly enhances the fluorescence upon aggregation. Single‐crystal X‐ray diffraction analysis confirmed that C?H???F, F???F, C?H???nitrile, Ar???Ar_F (Ar=aryl, Ar_F=fluoroaryl), and nitrile???Ar_F intra‐ and intermolecular interactions drive the topology of the molecule and that solid‐state supramolecular contacts favor AIE of the furan derivatives.     

Mixed‐Metal Coordination Cages Constructed with Pyridyl‐Functionalized β‐Diketonate Metalloligands: Syntheses,Structures and Host–Guest Properties

The design and synthesis of mixed‐metal coordination cages, which can act as hosts to encapsule guest molecules, is a subject of intensive research, and the utilization of metalloligand is an effective method to construct a designed heterometallic architecture. Herein, a series of heterometallic cages with half‐sandwich Rh, Ir and Ru fragments using Cu^II‐metalloligand as a building block by a stepwise approach is reported. The cavity sizes of the cages could be controlled easily by the lengths of the organic ligands. Because the metalloligands in the oxalate‐based cage are somewhat distorted and concave, there are weak Cu???O interactions in the molecules, forming a binuclear copper unit. By increasing the height of the cages using longer ligands, 2,5‐dichloro‐3,6‐dihydroxy‐1,4‐benzoquinone (H₂CA), the organometallic boxes display interesting host–guest behavior, which are made large enough to accommodate some large molecules, such as pyrene and [Pt(acac)₂]. Interestingly, the heterometallic cage with larger cavity size can transfer into a homometallic hexanuclear prism in the presence of pyrazine.     

Planar 2‐Pyridyl‐1,2,3‐triazole Derived Metallo‐ligands: Self‐assembly with PdCl2 and Photocatalysis

Self‐assembled metallosupramolecular architectures (MSAs) with built‐in functionalities such as light‐harvesting metal centers are a promising approach for developing emergent properties within discrete molecular systems. Herein we describe the synthesis of two new but simple “click” ligands featuring a bidentate 2‐pyridyl‐1,2,3‐triazole chelate pocket linked to a monodentate pyridyl (either 3‐ or 4‐substituted, L1 and L2 ) unit. The ligands and the corresponding four Pd^IIand Pt^IImetallo‐ligands ( Pd1 , Pd2 , Pt1 and Pt2 ) were synthesized and characterized using nuclear magnetic resonance (NMR) spectroscopy, electrospray ionization mass spectrometry (ESI‐MS), and X‐ray crystallography. Solid‐state characterization of the series of ligands and metallo‐ligands revealed that these compounds display a co‐planar conformation of all the aryl units. The Pt^IIcontaining metallo‐ligands ( Pt1 and Pt2 ) were found to assemble into square ( Sqr ) and triangular ( Tri ) shaped architectures when combined with neutral PdCl₂ linker units. Additionally, the ability of the Pt^IImetallo‐ligands and Tri to photocatalyze the cycloaddition of singlet oxygen to anthracene was investigated.     

Metal-induced supramolecualr chirality in an optically active polythiophene aggregate

Chiral polythiophenes (PTs), in sharp contrast to other optically active polymers, exhibit optical activity in the pi-pi* transition region which is derived from the chirality of the main chain when they self-assemble to form a supramolecular pi-stacked aggregate with intermolecular interactions in a poor solvent or in a film. We now report that the regioregular, optically active PT poly[(R)-3-[4-(4-ethyl-2-oxazolin-2-yl)phenyl]thiophene] (poly-1) exhibits unique split-type induced circular dichroism (ICD) in the pi-pi* transition region of the main chain upon complexation with various metal salts such as trifluoromethanesulfonates of copper(I), copper(II), silver(I), and zinc(II), and iron(II) perchlorate in chloroform, which is a good solvent for poly-1. The appearance of ICD and slight changes in the UV/Vis spectra (no color change), except for the zinc salts, indicated that the chirality may not be induced by chiral pi-stacked aggregates of poly-1, but by the chirality of the main chain, for example, a predominantly one-handed helical structure induced by intermolecular coordination of the oxazoline groups to metal ions. The sign of the Cotton effect depends on the metal salt; most metal salts induced ICDs with similar Cotton-effect patterns, while zinc salts caused an inversion of the signs of the Cotton effect of poly-1 accompanied by a gradual red shift in the absorption of up to 125 nm. The changes in the conformation and the size of the poly-1 aggregates induced by different metal salts were also investigated by (1)H NMR titrations, static light scattering (SLS), atomic force microscopy (AFM), and membrane filtration. On the basis of these results, we propose a possible model for the chiral supramolecular aggregates of poly-1 with metal salts.     

Chiral transformation: from single nanowire to double helix

We report a new type of water-soluble ultrathin Au-Ag alloy nanowire (NW), which exhibits unprecedented behavior in a colloidal solution. Upon growth of a thin metal (Pd, Pt, or Au) layer, the NW winds around itself to give a metallic double helix. We propose that the winding originates from the chirality within the as-synthesized Au-Ag NWs, which were induced to untwist upon metal deposition.