Slippage of a Porphyrin Macrocycle over Threads of Varying Bulkiness: Implications for the Mechanism of Threading Polymers through a Macrocyclic Ring

Threading of a polymer through a macrocyclic ring may occur directly, that is, by finding the end of the polymer chain, or by a process in which the polymer chain first folds and then threads through the macrocyclic ring in a hairpin‐like conformation. We present kinetic and thermodynamic studies on the threading of a macrocyclic porphyrin receptor ( H₂1 ) onto molecular threads that are blocked on one side and are open on the other side. The open side is modified by groups that vary in ease of folding and in bulkiness. Additionally, the threads contain a viologen binding site for the macrocyclic receptor, which is located close to the blocking group. The rates of threading of H₂1 were measured under various conditions, by recording as a function of time the quenching of the fluorescence of the porphyrin, which occurs when receptor H₂1 reaches the viologen binding site. The kinetic data suggest that threading is impossible if the receptor encounters an open side that is sterically encumbered in a similar way as a folded polymer chain. This indicates that threading of polymers through macrocyclic compounds through a folded chain mechanism is unlikely.     

Enantioselective synthesis of chiral porphyrin macrocyclic hosts and kinetic enantiorecognition of viologen guests

The construction of macromolecular hosts that are able to thread chiral guests in a stereoselective fashion is a big challenge. We herein describe the asymmetric synthesis of two enantiomeric C₂-symmetric porphyrin macrocyclic hosts that thread and bind different viologen guests. Time-resolved fluorescence studies show that these hosts display a factor 3 kinetic preference (ΔΔG^‡_on = 3 kJ mol⁻¹) for threading onto the different enantiomers of a viologen guest appended with bulky chiral 1-phenylethoxy termini. A smaller kinetic selectivity (ΔΔG^‡_on = 1 kJ mol⁻¹) is observed for viologens equipped with small chiral sec-butoxy termini. Kinetic selectivity is absent when the C₂-symmetric hosts are threaded onto chiral viologens appended with chiral tails in which the chiral moieties are located in the centers of the chains, rather than at the chain termini. The reason is that the termini of the latter guests, which engage in the initial stages of the threading process (entron effect), cannot discriminate because they are achiral, in contrast to the chiral termini of the former guests. Finally, our experiments show that the threading and de-threading rates are balanced in such a way that the observed binding constants are highly similar for all the investigated host–guest complexes, i.e. there is no thermodynamic selectivity.

Chiral guests display kinetic stereoselective threading through chiral porphyrin cages if their chirality is located at the chain ends and not in the centers, supporting the previously reported entron effect of threading.     

NMR structural analysis of a modular threading tetraintercalator bound to DNA

The synthesis and NMR structural studies are reported for a modular threading tetraintercalator bound to DNA. The tetraintercalator design is based on 1,4,5,8-tetracarboxylic naphthalene diimide units connected through flexible peptide linkers. Aided by an overall C(2) symmetry, NMR analysis verified a threading polyintercalation mode of binding, with linkers alternating in the order minor groove, major groove, minor groove, analogous to how a snake might climb a ladder. This study represents the first NMR analysis of a threading tetraintercalator and, as such, structurally characterizes a new topology for molecules that bind to relatively long DNA sequences with extensive access to both DNA grooves.     

A Highly Oxidized Cobalt Porphyrin Dimer: Spin Coupling and Stabilization of the Four‐Electron Oxidation Product

A highly oxidized cobalt porphyrin dimer is reported. Each cobalt(II) ion and porphyrin ring underwent 1e oxidation with iodine as the oxidant to give a 4e‐oxidized cobalt(III) porphyrin π‐cation radical dimer. The bridging ethylene group allows for substantial conjugation of the porphyrin macrocycles, thus leading to a strong antiferromagnetic coupling between the π‐cation radicals and to stabilization of the singlet state. X‐ray crystallography clearly showed that the complex may be considered as a real supramolecule rather than two cobalt(III) porphyrin π‐cation radicals that interact through space.     

Glutathione as the end capper for cyclodextrin/PEG polyrotaxanes

A facile one-pot synthesis of α-cyclodextrin-based polyrotaxane(PR) in aqueous solution is reported, where the peptide glutathione was used as the end-capping agent and the thiol-ene Michael addition was used as the end-capping reaction. Both polyrotaxanes with low threading ratio and high threading ratio were successfully obtained. In contrast to the conventionally used multiple-step synthesis methods and hydrophobic end cappers, this one-pot aqueous synthesis as well as the biocompatibility of the end-capping agent could result in a much more biocompatible PR to be used as biomaterials.     

A Flexible Copper(I)‐Complexed [4]Rotaxane Containing Two Face‐to‐Face Porphyrinic Plates that Behaves as a Distensible Receptor

A new cyclic [4]rotaxane composed of two flexible bis‐macrocycles and two rigid axles is described. Each bis‐macrocycle consists of two rings attached to antipodal meso positions of a central Zn porphyrin through single C? C bonds. Each ring incorporates a 2,9‐diphenyl‐1,10‐phenanthroline chelation site. The axles contain two coplanar bidentate sites derived from the 2,2′‐bipyridine motif. The building blocks were assembled by using a one‐pot threading‐and‐stoppering reaction, which afforded the [4]rotaxane in 50 % yield. The “gathering‐and‐threading” effect of copper(I) was utilised in the formation of a [4]pseudorotaxane, which was immediately converted to the corresponding [4]rotaxane by a quadruple CuAAC stoppering reaction. The rotaxane contains two face‐to‐face zinc porphyrins, which allowed the coordination of ditopic guest substrates. The rotaxane host showed remarkable flexibility and was able to adjust its conformation to the guest size. It can be distended and accommodate rod‐like guests of 2.6 to 15.8 Å in length.     

Investigation of the SERS behaviour of porphyrins with different surface concentrations on electrochemically prepared Ag-surface

Surface-enhanced Raman scattering (SERS) spectra, taken with 632.8 nm excitation are reported for the water-soluble tetrakis(3-N-methylpyridyl)porphyrin chloride (TMPyP(3)), tetrakis(4-N-methylpyridyl)porphyrin chloride (TMPyP(4)) and Sn(IV)tetrakis(4-N-methylpyridyl)porphyrin chloride (Sn(IV)TMPyP(4)) using an electrochemically prepared Ag surface with an area ca. 12.56 mm2. It was found that the spectra vary as increasing amounts of the compounds are placed on the surface, with surface concentrations in the approximate range 1000-5 pmol/12.56 mm2. We suggest that the reasons for the changes be that the reaction means between porphyrin molecules and Ag surface is different and the porphyrin macrocyclic molecules adopt different orientation as the surface concentrations decrease.     

Modification of statistical threading in two-component pseudorotaxane melts using the amphiphilic approach and variations in the confinement geometry

Recently we described a coarse-grained model of poly(ethylene oxide) and then employed that model to study the amount of spontaneous threading of cyclic molecules by linear chains in the melt [C. A. Helfer, G. Xu, W. L. Mattice, and C. Pugh, Macromolecules 36, 10071 (2003)]. Since the amount of statistical threading at equilibrium is small, there is interest in identifying physical changes in the system that will increase the threading. We now use that coarse-grained model to investigate the effect on threading of various hypothetical (but feasible) modifications to the two-component system of macrocycles and linear chains in the melt, and different confinement geometries, that can bring about correlations in the arrangement of the rings. Our work follows on the concept of an amphiphilic approach [C. Pugh, J.-Y. Bae, J. R. Scott, and C. L. Wilkins, Macromolecules 30, 8139 (1997)] for increasing the statistical threading in homopolyrotaxane melts. We investigate whether introducing such correlations in the macrocycles can increase the spontaneous threading. This paper shows that some of our modifications can yield more than double the amount of threading seen in purely statistical mixing.     

Metal Linkage Effects on Ultrafast Energy Transfer

We report the preparation of several new porphyrin homodimers bridged by a platinum(II) ion in which very intense electronic communication through the coordination link occurs. Moreover, the synthesis of a new porphyrin dyad and its photophysical properties are reported. This dyad exhibits the fastest singlet energy transfer ever reported for synthetic systems between a zinc(II) porphyrin and a porphyrin free base. This extremely fast transfer (～100 femtoseconds) is in the same range as the fastest one measured in natural systems. This feature is due to the platinum(II) linker, which allows for strong MO couplings between the two porphyrin units as experimentally supported by electrochemistry and corroborated by DFT computations.     

Changing DNA grooves--a 1,4,5,8-naphthalene tetracarboxylic diimide bis-intercalator with the linker (beta-Ala)(3)-Lys in the minor groove

We have been investigating a modular, threading DNA polyintercalator design based upon the 1,4,5,8-naphthalene tetracarboxylic diimide (NDI) intercalating unit. Previously, we have reported the NMR analysis of a bis-intercalator-DNA complex in which the peptide linker between NDI units was found to occupy the DNA major groove (Guelev, Lee, Sorey, Hoffman, Iverson, Chem. Biol. 2001, 8, 415-425). Here we describe the NMR analysis of a complex between a related bis-intercalator known to display altered DNA sequence specificity. In this case, the linker resides in the DNA minor groove. We have thus shown that within this set of sequence specific bis-intercalators, both DNA grooves can be accessed, setting the stage for longer threading polyintercalators designed to have linkers occupying both grooves in an alternating fashion.     

Kinetic characterization of an extremely slow DNA binding equilibrium

We here exploit the recently reported thermodynamic preference for poly(dAdT)(2) over mixed-sequence calf thymus (ct) DNA of two binuclear ruthenium complexes, DeltaDelta-[mu-bidppz(bipy)4Ru2](4+) (B) and DeltaDelta-[mu-bidppz(phen)(4)Ru(2)](4+) (P), that bind to DNA by threading intercalation, to determine their intrinsic dissociation rates. After adding poly(dAdT)(2) as a sequestering agent to B or P bound to ct-DNA, the observed rate of change in luminescence upon binding to the polynucleotide reflects the rate of dissociation from the mixed sequence. The activation parameters for the threading and dissociation rate constants allow us for the first time to characterize the thermodynamics of the exceedingly slow threading intercalation equilibrium of B and P with ct-DNA. The equilibrium is found to be endothermic by 33 and 76 kJ/mol, respectively, and the largest part of the enthalpy difference between the complexes originates from the forward threading step. At physiological temperature (37 degrees C) B and P have dissociation half-lives of 18 and 38 h, respectively. This is to our knowledge the slowest dissociating noncovalently bound DNA-drug reported. SDS sequestration is the traditional method for determination of rate constants for cationic drugs dissociating from DNA. However, the rates may be severely overestimated for slowly dissociating molecules due to unwanted catalysis by the SDS monomers and micelles. Having determined the intrinsic dissociation rates with poly(dAdT)(2) as sequestering agent, we find that the catalytic effect of SDS on the dissociation rate may be up to a factor of 60, and that the catalysis is entropy driven. A simple kinetic model for the SDS concentration dependence of the apparent dissociation rate suggests an intermediate that involves both micelles and DNA-threaded complex.     

Photoinduced electron transfer in Zn(II)porphyrin-bridge-Pt(II)acetylide complexes: variation in rate with anchoring group and position of the bridge

The synthesis and photophysical characterization of two sets of zinc porphyrin platinum acetylide complexes are reported. The two sets of molecules differ in the way the bridging phenyl-ethynyl unit is attached to the porphyrin ring. One set is attached via an ethynyl unit on the β position, while the other set is attached via a phenyl unit on the meso position of the porphyrin. These were compared with previously studied complexes where attachment was made via an ethynyl unit on the meso position. Femtosecond transient absorption measurements showed in all systems a rapid quenching of the porphyrin singlet state. Electron transfer is suggested as the quenching mechanism, followed by an even faster recombination to form both the porphyrin ground and triplet excited states. This is supported by the variation in quenching rate and porphyrin triplet yield with solvent polarity, and the observation of an intermediate state in the meso-phenyl linked systems. The different linking motifs between the dyads resulted in significant variations in electron transfer rates.     

并入两个四氢键组装单体的卟啉衍生物的合成研究

报道了一个新的卟啉四氢键超分子聚合物组装单体29的合成研究。通过对 Gong等最近报道的四氢键二聚体组装板块进行修饰，合成了两个相应的新的苯甲酸 衍生物中间体11和21，以间－硝基苯甲醛为原料以较高产率合成了一个二硝基四苯 基卟啉26，氯化亚锡还原得到另－卟啉二胺中间体28。以DCC为缩合剂，该卟啉二 胺与其中一个酸11发生缩合反应得到相应卟啉组装单体目标分子29。化合物29在弱 极性溶剂中具有良好的溶解度。     

Control of the geometry of the adsorbed thin layer by the depletion interaction

The depletion interaction was reported to drive the mixtures of rodlike colloids and polymer coils into a variety of phase transitions such as isotropic-nematic, nematic-smectic, and so forth. We describe in this Communication a convenient preparation of the self-assembled monolayer of the platelike porphyrin molecules by the depletion interaction between the absorbent and the metal substrates. After the depletant, low molecular weight poly(ethylene oxide) (PEO), was added into the porphyrin/ethanol solution, random oriented porphyrin was then regulated to lie parallel to the adjacent metal substrates, forming the self-assembled monolayer.     

Quinoxalino[2,3-b']porphyrins behave as pi-expanded porphyrins upon one-electron reduction: broad control of the degree of delocalization through substitution at the macrocycle periphery

The synthesis and redox properties of a series of free-base and metal(II) quinoxalino[2,3-b']porphyrins and their use in an investigation of the substituent effects on the degree of communication between the porphyrin and its beta,beta'-fused quinoxalino component are reported. ESR, thin-layer spectroelectrochemistry, and quantum chemical calculations of the resultant radical anions from one-electron reduction indicate that localization of the unpaired electron across both the porphyrin and the fused quinoxalino group can be controlled, the system as a whole behaving as a highly polarizable pi-expanded porphyrin radical anion. ESR studies on the radical anions of zinc(II) quinoxalino[2,3-b']porphyrin derivatives indicate that nitrogen-atom spin distribution changes as a function of chemical substitution: 27% quinoxaline character when the porphyrin ring bears a 7-nitro substituent, 34% quinoxaline character in the unsubstituted parent, and 51-61% nitroquinoxaline character when the quinoxalino unit has one or more nitro groups. Close analogies are found between the calculated and observed nitrogen-atom spin distributions, indicating that the calculations embody the key chemical effects. The calculations also indicate that the nitrogen-atom spin distributions closely parallel the important total porphyrin, quinoxaline, and nitro spin distributions, indicating that the observed quantities realistically depict the change in the nature of the delocalization of the radical anion as a function of chemical substitution. The profound effects observed indicate long-range communication of the type that is essential in molecular electronics applications.     

Structural and vibrational properties of tetraoxaporphyrin dication, the oxygen analogue of porphyrin, and of isoelectronic diprotonated porphyrin

Structural calculations by means of the density functional method have been performed on tetraoxaporphyrin dication and on isoelectronic diprotonated porphyrin as well as on the sulfur and carbon analogues of porphyrin. A detailed study of the stable conformations of these compounds is reported starting with the most symmetrical conformations and lowering the symmetry along the vibrational coordinates with imaginary frequency. The calculated geometries are related to experimental structures available from X-ray diffraction studies. The Raman spectra of tetraoxaporphyrin dication exciting with micro-Raman instrumentation at 785 nm and of diprotonated porphyrin in near-resonance conditions with the Soret band have been measured. The correlation between frequencies calculated with the DF/B3-LYP/cc-pVDZ procedure for porphyrin, diprotonated porphyrin, and tetraoxaporphyrin dication has allowed for making a vibrational assignment for the latter two systems in excellent agreement with experiment using a single frequency scale factor.     

Novel methodology to control the adsorption structure of cationic porphyrins on the clay surface using the "size-matching rule"

Saponite-type clays that have different cation exchange capacities were successfully synthesized by hydrothermal synthesis. The structure and properties were analyzed by X-ray diffraction, X-ray fluorescence, (27)Al NMR, FT-IR, thermogravimetric and differential thermal analysis, atomic force microscopy, and cation exchange capacity measurement. The intercharge distances on the synthetic saponite (SS) surfaces were calculated to be 0.8-1.9 nm on the basis of a hexagonal array. The complex formation behavior between SS and cationic porphyrins was examined. It turns out that the average intermolecular distance between porphyrin molecules on the SS surface can be controlled, depending on the charge density of the SS. In the case of tetrakis(1-methylpyridinium-4-yl)porphyrin (H(2)TMPyP(4+)), the average intermolecular distances on the SS surface can be controlled from 2.3 to 3.0 nm on the basis of a hexagonal array. It was also found that absorption maxima of porphyrins depend on the charge density of the SS. The adsorption behavior of porphyrin on the SS surface can be rationally understood by the previously reported "size-matching rule". This methodology using host-guest interaction can realize a unique adsorption structure control of the porphyrin molecule on the SS surface, where the gap distance between guest porphyrin molecules is rather large. These findings will be highly valuable to construct photochemical reaction systems such as energy transfer in the complexes.     

Synthesis of Unsymmetrical Schiff-Base Porphyrin with O-Nitrobenzaldehyde and its Lanthanide Complexes

The synthesis of a new unsymmetrical Schiff-base porphyrin is reported from 5-(p-nitrophenyl)-10, 15, 20-triphenyl porphyrin and o-nitro benzaldehyde. Its lanthanide complexes are also reported. The ligand and its lanthanide complexes are characterized by UV, IR and ¹H NMR spectra.     

Self-sorting under solvent-free conditions: one-pot synthesis of a hetero[3]rotaxane

The one-pot synthesis of a hetero[3]rotaxane, assembled from five different molecular components under solvent-free conditions, through "self-sorting" of the bead and stopper units during the threading and stoppering processes, is reported.     

Strong Induced‐Fit Binding of Viologen and Pyridine Derivatives in Adjustable Porphyrin Cavities

The synthesis and binding properties of new porphyrin cage compounds consisting of a rigid diphenylglycoluril part, which is connected via flexible bis(ethyleneoxy) spacers to a (metallo)porphyrin “roof”, are reported. Binding of viologen guests and pyridine ligands in these porphyrin cages are accompanied by significant conformational reorganizations of the hosts. Despite these structural changes, association constants are still very high, revealing that not only receptors that bind guests according to a lock‐and‐key mechanism but also those that bind guests by an induced‐fit mechanism can exhibit strong binding.