Metal vs Ligand Oxidation: Coexistence of Both Metal-Centered and Ligand-Centered Oxidized Species.

A series of two-electron-oxidized cobalt porphyrin dimers have been synthesized upon controlled oxidations using halogens. Rather unexpectedly, X-ray structures of two of these complexes contain two structurally different low-spin molecules in the same asymmetric unit of their unit cells: one is the metal-centered oxidized diamagnetic entity of the type CoIII(por), while the other one is the ligand-centered oxidized paramagnetic entity of the type CoII(por•+). Spectroscopic, magnetic, and DFT investigations confirmed the coexistence of the two very different electronic structures both in the solid and solution phases and also revealed a ferromagnetic spin coupling between Co(II) and porphyrin π-cation radicals and a weak antiferromagnetic coupling between the π-cation radicals of two macrocycles via the bridge in the paramagnetic complex.

Reversible open-closed conformational switching of nano-size metalloporphyrin dimers triggered by light and temperature.

The current work demonstrates the reversible control of substantial molecular motion in 'nano-sized' molecules, where two structural isomers can 'open' and 'close' their cavities in response to light or heat. The isomers differ widely in their photophysical properties, including colour, polarity, two-photon absorption and π-conjugation, and can easily be separated through column chromatography and thus have wide applicability.

Unusual Stabilisation of Remarkably Bent Tetra-Cationic Tetra-radical Intermolecular Fe(III) µ-Oxo Tetranuclear Complexes.

A hitherto unknown series of air stable, π-conjugated, remarkably bent tetra-cation tetra-radical intermolecular Fe(III) µ-oxo tetranuclear complex, isolated from the dication diradical diiron(III) porphyrin dimers, has been synthesised and spectroscopically characterised along with single crystal X-ray structure determination of two such molecules. These species facilitate long-range charge/radical delocalisation through the bridge across the entire tetranuclear unit manifesting an unusually intense NIR band. Assorted spin states of Fe(III) centres are stabilised within these unique tetranuclear frameworks: terminal six-coordinate iron centres stabilise the admixed intermediate spin states while the central five-coordinate iron centres stabilise the high-spin states. Variable temperature magnetic susceptibility measurements indicated strong antiferromagnetic coupling for the Fe(III)-O-Fe(III) unit while the exchange interactions between the Fe centres and the porphyrin π-cation radicals are weaker as supported both by magnetic data and DFT calculations. The nature of orbital overlap between the SOMOs of Fe(III) and π* orbital of the porphyrin was found to rationalise the observed exchange coupling, establishing such a complex magnetic exchange in this tetranuclear model with a significant bioinorganic relevance.

Spin-Flip via Subtle Electronic Perturbation in Axially Ligated Diiron(III) Porphyrin Dimer.

Spin state switching in the metal center is a crucial phenomenon in many enzymatic reactions in biology. The spin state alteration, a critical step in cytochrome P450 catalysis, is driven most likely through a weak perturbation upon substrate binding in the enzyme, which is still not well clarified. In the current work, the spin state transition of iron(III) from high to intermediate via an admixed state is observed upon a subtle electronic perturbation to the sulphonate moieties coordinated axially to a diiron(III)porphyrin dimer. While electron-donating substituents stabilize the high-spin state of iron(III), strongly electron-withdrawing groups stabilize an intermediate-spin state, whereas the moderate electron-withdrawing nature of axial ligands resulted in an admixed state. Confirmation of the molecular structures and their spin states have been made utilizing single-crystal X-ray structure analysis, Mössbauer, magnetic, EPR, and 1H NMR spectroscopic investigations. The position of the signals of the porphyrin macrocycle in the paramagnetic 1H NMR is found to be very characteristic of the spin state of the iron center in solution. The Curie plot for the pure high-spin complexes shows the signals' temperature dependency in line with the Curie law. Conversely, the pure intermediate-spin state of iron exhibits an anti-Curie temperature dependence, whereas the admixed-spin state of iron displays significant curvature of the lines in the Curie plot. An extensive DFT analysis displays a linear dependence between the energy difference between d x 2 - y 2 ${{_{x{^{2}}- y{^{2}}}}}$ and d z 2 ${{_{z{^{2}}}}}$ orbital versus Fe-Npor distance for the complexes reported here. Furthermore, a strong linear correlation between the Fe-O distance and the spin density over the oxygen atom, as well as the Fe-Npor distance for the complexes, has been observed. Thus, a slight electronic perturbation at the axial ligand of the diheme resulted in a large change in the electronic structures with a spin-flip. This is at par with the metalloenzymes, which employ minute perturbations around the periphery of the active sites, leading to spin state transitions.

Stable Dication Diradicals of Triply Fused Metallo Chlorin-Porphyrin Heterodimers: Impact of the Bridge on the Control of Spin Coupling to Reactivity.

We report an unexpected rearrangement, controlled by the nature of the bridge, leading to the formation of novel, remarkably stable triply fused dinickel(II)/dicopper(II) chlorin-porphyrin dication diradical heterodimers in excellent yields. Here, a dipyrromethene bridge gets completely fused between two porphyrin macrocycles with two new C-C and one C-N bonds. The two macrocycles exhibit extensive π-conjugation through the bridge, which results in an antiferromagnetic coupling between the two π-cation radicals. In addition, the macrocyclic distortion also favours a rare intramolecular ferromagnetic interaction between the CuII and π-cation radical spins to form a triplet state. The structural and electronic perturbation in the unconjugated dication diradical possibly enables the bridging pyrrolic nitrogen to undergo a nucleophilic attack at the nearby ß-carbon of the porphyrin π-cation radical with a computed free energy barrier of >20 kcal mol-1 which was supplied in the form of reflux condition to initiate such a rearrangement process. UV-vis, EPR and ESI-MS spectroscopies were used to monitor the rearrangement process in situ in order to identify the key reactive intermediates leading to such an unusual transformation.

Modulation of iron spin states in highly distorted iron(III) porphyrins: H-bonding interactions and implications in hemoproteins.

A family of five- and six-coordinated Fe-porphyrins which enable us to scrutinize the effects of non-covalent interactions on the out-of-plane displacement of iron and its spin-states and axial ligand orientation in a single distorted macrocyclic environment has been reported. Combined analysis using single-crystal X-ray structure determination and EPR spectral investigation revealed the stabilization of the high-spin state of iron in the five-coordinate complex FeIII(TPPBr8)(OCHMe2), while six-coordinate complexes [FeIII(TPPBr8)(MeOH)2]ClO4, [FeIII(TPPBr8)(H2O)2]ClO4 and [FeIII(TPPBr8)(1-MeIm)2]ClO4 stabilize admixed-high, admixed-intermediate and low-spin states, respectively. The H-bonding interactions between the weak axial H2O/MeOH and perchlorate anion resulted in an elongation of the Fe-O bond which eventually shortened the Fe-N(por) distances leading to the stabilization of the admixed spin state of iron which, otherwise, stabilizes the high-spin (S = 5/2) state only. In addition, the iron atom in [FeIII(TPPBr8)(H2O)2]ClO4 is displaced by 0.02 Å towards one of the water molecules engaged in the H-bonding interactions leading to two different Fe-O (H2O) distances of 2.098(8) and 2.122(9) Å. In contrast, iron in [FeIII(TPPBr8)(MeOH)2]ClO4 sits on the plane of the porphyrin since both the axial methanol units are engaged in similar H-bonding interactions with the ClO4- ion. Moreover, the X-ray structure of low-spin FeII(TPPBr8)(1-MeIm)2 revealed a dihedral angle of 63.0° between two imidazoles which deviates largely from the expected angle of 90° (perpendicular orientations) since the axial imidazole protons are engaged in strong intermolecular C-H⋯π interactions which thereby restrict the axial ligand movement. The complex also displays the shortest Fe-N(1-MeIm) bond along with smallest dihedral angles of 7.8° and 22.4° between the axial imidazole ring and the closest Fe-Np axis due to strong π-interactions between iron and the axial imidazole ligand. Our work highlights the influence of non-covalent interactions on the out-of-plane displacement and spin state of iron and axial ligand orientations which are indeed important steps in the functioning of various hemoproteins.

Modulation of supramolecular chirality by stepwise axial coordination in a nano-size trizinc(ii)porphyrin trimer.

Herein, we report a chiral guest's triggered spring-like contraction and extension motions coupled with unidirectional twisting in a novel flexible and 'nano-size' achiral trizinc(ii)porphyrin trimer host upon step-wise formation of 1 : 1, 1 : 2, and 1 : 4 host-guest supramolecular complexes based on the stoichiometry of the diamine guests for the first time. During these processes, porphyrin CD responses have been induced, inverted, and amplified, and reduced, respectively, in a single molecular framework due to the change in the interporphyrin interactions and helicity. Also, the sign of the CD couplets is just the opposite between R and S substrates which suggests that the chirality is dictated solely by the stereographic projection of the chiral center. Interestingly, the long-range electronic communications between the three porphyrin rings generate trisignate CD signals that provide further information about molecular structures.

Diheme cytochromes: Effect of mixed-axial ligation on the electronic structure and electrochemical properties with cobalt porphyrin dimer.

A series of six-coordinate diCo(III) porphyrin dimers, as synthetic analogues of diheme cytochromes, have been reported here having bis(imidazole), bis(pyridine) and mixed thiophenolate-pyridine/imidazole axial ligands. In the X-ray structures of bis(imidazole) and bis(pyridine) complexes, the axial ligands are in perpendicular orientation while they are parallelly oriented in their monomeric analog. The porphyrin rings are also highly ruffle-distorted in dimer but planar in monomer which reflect the effect of intramolecular interaction between two Co(porphyrin) units in dimers. In the X-ray structure of diCo(III) thiophenolate-pyridine mixed-ligated complex, the axial Co-S and Co-N(py) distances are 2.256(1) and 2.063(2) Å, respectively. The Co-N(py) distance of 2.063(2) Å is much longer than the distances of 1.961(3) and 1.972(3) Å observed in bis(pyridine) complex and the Co-S distance is larger than Co-N(py) in the mixed ligated complex which results in a displacement of Co by 0.15 Štowards the pyridine ligand from the mean porphyrin plane. Indeed, this is the first X-ray structure of a metalloporphyrin with mixed thiophenolate-pyridine axial ligands. The effect of mixed-axial ligation is demonstrated by a blue-shift of the Soret band in the UV-visible spectroscopy and also a positive shift of the Co(III)/Co(II) redox couple as compared to their bis(pyridine) analogue. The redox potentials are shifted to a large negative value just upon replacing the metal from iron to cobalt. The present investigation emphasizes the role of axial ligation, metal ions, and also the effect of heme-heme interaction in controlling the spectral and electrochemical properties.

Control of spin coupling through a redox-active bridge in a dinickel(II) porphyrin dimer: step-wise oxidations enable isolations of a chlorin-porphyrin heterodimer and a dication diradical with a singlet ground state.

A dinickel(II)porphyrin dimer has been used here in which the redox-active pyrrole-moiety, similar to the tryptophan residue in diheme enzymes such as MauG and bCcP, has been placed between two Ni(II)porphyrin centers connected via a flexible, but unconjugated methylene bridge. This arrangement provides a large physical separation between the two metal centers and thus displays almost no communication between them through the bridge. Upon treatment with DDQ as an oxidant, the dinickel(II) porphyrin dimer slowly gets converted into an indolizinium-fused chlorin-porphyrin heterodimer. However, oxidations of the dinickel(II) porphyrin dimer up to two oxidizing equivalents using oxidants such as AgSbF6 and FeCl3 resulted in the formation of a dication diradical complex. Interestingly, in order to stabilize such a highly oxidized dication diradical, two non-conjugated methylene spacers undergo facile 2e-/-2H+ oxidation to make the bridge fully π-conjugated for promoting through-bond communication. Through the oxidized and conjugated bridge, two porphyrin π-cation radicals display considerable communications leading to an efficient intramolecular spin coupling to form a singlet state. Interestingly, the redox-active nature of the bridge controls the electronic communication just by simple oxidation or reduction, and thereby, acts as a molecular switch for efficient magnetic relay.

Induction and rationalization of supramolecular chirality in a highly flexible Zn(II)porphyrin dimer: structural, spectroscopic and theoretical investigations.

A highly flexible pyrrole-bridged Zn(II)porphyrin dimer has been successfully utilized as an efficient host which enables an accurate determination of the absolute configuration directly for a large number of chiral amino alcohols and 1,2-diols. The addition of substrates resulted in the formation of 1 : 1 sandwich complexes which, after the addition of excess substrates, produced 1 : 2 host-guest complexes. In principle, the 1 : 2 host-guest complexes can be stabilized in three possible conformations, viz. exo-exo, exo-endo, and endo-endo based on how a substrate binds to the metal. The endo-endo conformation is stabilized by two strong interligand H-bonds [O-H⋯O(H)] between encapsulated diols which thereby interlock the stereochemistry. In the absence of such interligand H-bonding interactions, exo-endo binding is preferred as it is indeed observed for amino alcohols which show weaker CD couplets due to the free movement of substrates. The sandwich complexes with amino alcohols show a more intense CD couplet compared to the diols due to the stronger binding of the amine functionality (-NH2) towards a Zn-atom over an alcoholic moiety (-OH). The CD amplitude showed linear dependence with a binding constant for the 1 : 1 sandwich complex upon varying the substrates. Spectroscopic investigations, single crystal X-ray structure determination of four such host-guest complexes and DFT studies have enabled us to rationalize systematically the origin of optical activity unambiguously in the 1 : 1 and 1 : 2 host-guest complexes, which lead to an absolute stereochemical determination of a large number of chiral substrates. The larger vertical and horizontal flexibility of a diethyl pyrrole spacer induces stronger binding of the substrates to form the 1 : 1 complex with a much larger torsional angle along with intense CD couplets. In contrast, a rigid dibenzothiophene-bridged tweezer, due to its limited horizontal and vertical flexibility, facilitates 1 : 2 complexation more as compared to the highly flexible pyrrole-bridged host which results in stronger binding of the substrate with the intense CD couplet for the former.

Highly Oxidized Cobalt Porphyrin Dimer: Control of Spin Coupling via a Bridge.

A cobalt porphyrin dimer is constructed in which two Co(II)porphyrins are connected covalently through a redox-active diethylpyrrole moiety via a flexible but "nonconjugated" methylene bridge. Upon oxidation with even a mild oxidant such as iodine, each cobalt(II) center and porphyrin ring undergo 1e- oxidation, leading to the formation of a 4e--oxidized cobalt(III)porphyrin dication diradical complex. Other oxidants such as Cl2 and Br2 also produce similar results. To stabilize such highly oxidized dication diradicals, the "nonconjugated" methylene spacer undergoes a facile and spontaneous oxidation to form a methine group with a drastic structural change, thereby making the bridge fully π-conjugated and enabling through-bond communication. This results in a strong spin coupling between two π-cation radicals which stabilizes the singlet state. The experimental observations are also strongly supported by extensive density functional theory calculations. The present study highlights the crucial role played by the nature of the bridge in the long-range electronic communication.

Long-Range Intramolecular Spin Coupling through a Redox-Active Bridge upon Stepwise Oxidations: Control and Effect of Metal Ions.

Dinickel(II) and dicopper(II) porphyrin dimers have been constructed in which two metalloporphyrin units are widely separated by a long unconjugated dipyrrole bridge. Two macrocycles are aligned somewhat orthogonally to each other, while oxidation of the bridge generates a fully π-conjugated butterfly-like structure, which, in turn, upon stepwise oxidations by stronger oxidants result in the formation of the corresponding one- and two-electron-oxidized species exhibiting unusual long-range charge/radical delocalization to produce intense absorptions in the near-infrared (NIR) region and electron paramagnetic resonance (EPR) signals of a triplet state due to interaction between the unpaired spins on the Cu(II) ions. Although the two metal centers have a large physical separation through the bridge (more than 16 Å), they share electrons efficiently between them, behaving as a single unit rather than two independent centers. Detailed UV-vis-NIR, electrospray ionization mass spectrometry, IR, variable-temperature magnetic study, and EPR spectroscopic investigations along with X-ray structure determination of unconjugated, conjugated, and one electron-oxidized complexes have been exploited to demonstrate the long-range electronic communication through the bridge. The experimental observations are also supported by density functional theory (DFT) and time-dependent DFT calculations. The present study highlights the crucial roles played by a redox-active bridge and metal in controlling the long-range electronic communication.

Hydrogen-Bonding Interactions Trigger Induction of Chirality via Formation of a Cyclic Dimer.

A rationalization for the chirality transfer mechanism in the supramolecular host-guest assemblies of an achiral Zn(II) porphyrin dimer (host) and a series of chiral diamines and diamino esters (substrates) via cyclic dimer formation has been reported for the first time. Stepwise formations of 2:2 host-guest cyclic dimers and 1:2 host-guest monomeric complexes have been observed via intermolecular assembling and disassembling processes. A large bisignate CD couplet was observed for the cyclic dimer, whereas the monomeric complexes exhibited negligible CD intensity. Crystallographic characterizations demonstrate that the strong intermolecular H bonding in cyclic dimers is responsible for their stability over the linear chain, which thereby display high-intensity bisignate CD couplets. In order to minimize the steric crowding within the host-guest assembly, the cyclic dimer switches its helicity toward the conformer having less steric hindrance. The cyclic scaffold is oriented according to the pre-existing chirality of the substrate in both the solid and solution phases: the substrates having R chirality display a negative CD couplet, whereas the substrates with S chirality display a positive couplet. Opposite signs for the CD couplets between R and S substrates suggest that the stereographic projection at the chiral centers solely dictates the overall helicity of the cyclic dimer. DFT studies further support the experimental observations.

Ferromagnetic Coupling in Oxidovanadium(IV)-Porphyrin Radical Dimers.

Three different oxidovanadium(IV) porphyrin dimers with anti, cis, and trans arrangements of the two rings have been synthesized by changing the bridge between the porphyrin macrocycles. This provides a unique opportunity to investigate the role of the bridge and spatial arrangement between the two VIVO centers for their electronic communication and magnetic coupling. They were characterized by the combined application of XRD analysis, UV-vis and electron paramagnetic resonance (EPR) spectroscopy, cyclic voltammetry, magnetic susceptibility, and DFT calculations. One- and two-electron oxidations produce mono- and dication diradical species, respectively, which display an unusual ferromagnetic interaction between the unpaired spins of vanadium(IV) and porphyrin π-cation radical, in contrast to other metalloporphyrin dimers. The oxidized species show a dissimilar behavior between cis and trans isomers. The ferromagnetic coupling occurs between the porphyrin π-cation radical and the unpaired electron of the VIVO ion on the dxy orbital, orthogonal to the porphyrin-based molecular orbitals a1u and a2u.

Heme-Heme Interactions in Diheme Cytochromes: Effect of Mixed-Axial Ligation on the Electronic Structure and Electrochemical Properties.

Diheme cytochromes, the simplest members in the multiheme family, play substantial biochemical roles in enzymatic catalysis as well as in electron transfer. A series of diiron(III) porphyrin dimers have been synthesized as active site analogues of diheme cytochromes. The complexes contain six-coordinated iron(III) having thiophenol and imidazole at the fifth and sixth coordination sites, respectively. The iron centers in the complexes have been found to be in a low-spin state, as confirmed through solid-state Mössbauer and electron paramagnetic resonance (EPR) spectroscopic investigations. Mössbauer quadrupole splitting of complexes having mixed ligands is substantially larger than that observed when both axial ligands are the same. Rhombic types of EPR spectra with narrow separation between gx, gy, and gz clearly distinguish heme thiolate coordination compared to bis(imidazole)-ligated low-spin heme centers. The redox potential in diheme cytochromes has been found to be tuned by interheme interactions along with the nature of axial ligands. The effect of mixed-axial ligation within the diiron(III) porphyrin dimers is demonstrated by a positive shift in the Fe(III)/Fe(II) redox couple upon thiophenolate coordination compared to their bis(imidazole) analogues. The pKa of the imidazole also decides the extent of the shift for the Fe(III)/Fe(II) couple, while the potential of the mixed-ligated diiron(III) porphyrin dimer is more positive compared to their monomeric analogue. A variation of around 1.1 V for the Fe(III)/Fe(II) redox potential in the diiron(III) porphyrin dimer can be achieved with the combined effect of axial ligation and a metal spin state, while such a large variation in the redox potential, compared to their monomeric analogues, is attributed to the heme-heme interactions observed in dihemes. Moreover, theoretical calculations also support the experimental shifts in the redox potential values.

Through Bridge Spin Coupling in Homo- and Heterobimetallic Porphyrin Dimers upon Stepwise Oxidations: A Spectroscopic and Theoretical Investigation.

We have described copper(II)-iron(III) and copper(II)-manganese(III) heterobimetallic porphyrin dimers and compared them with the corresponding homobimetallic analogs. UV-visible spectra are very distinct in the heterometallic species while electrochemical studies demonstrate that these species, as compared to the homobimetallic analog, are much easier to oxidize. Combined Mössbauer, EPR, NMR, magnetic and UV-visible spectroscopic studies show that upon 2e-oxidation of the heterobimetallic complexes only ring-centered oxidation occurs. The energy differences between HOMO and LUMO are linearly dependent with the low-energy NIR band obtained for the 2e-oxidized complexes. Also, strong electronic communication between two porphyrin rings through the bridge facilitates coupling between various unpaired spins present while the coupling model depends on the nature of metal ions used. While unpaired spins of Fe(III) and the porphyrin π-cation radical are strongly antiferromagnetically coupled, such coupling is rather weak between Mn(III) and a porphyrin π-cation radical. Moreover, the coupling between two π-cation radicals are much stronger in the 2e-oxidized complexes of dimanganese(III) and copper(II)-manganese(III) porphyrin dimers as compared to their diiron(III) and copper(II)-iron(III) analogs. Furthermore, coupling between the unpaired spins of a π-cation radical and copper(II) is much stronger in the 2e-oxidized complex of copper(II)-iron(III) porphyrin dimer as compared to its copper(II)-manganese(III) analog. The Mulliken spin density distributions in 2e-oxidized homo- and heterobimetallic complexes show symmetric and asymmetric spread between the two macrocycles, respectively. In both the 2e-oxidized heterobimetallic complexes, the Cu(II) porphyrin center acts as a charge donor while Fe(III)/Mn(III) porphyrin center act as a charge acceptor. The experimental observations are also strongly supported by DFT calculations.

Hg···Hg···Hg Interaction Stabilizes Unusual Trinuclear Double Sandwich Structure of Mercury(II) Porphyrins.

For the first time, fully characterized and stable trinuclear "double sandwich" molecules are reported with Hg(II) ion using a highly flexible porphyrin dimer. The molecules display interesting and intense luminescence properties at room temperature. The present investigation clearly demonstrates that attractive mercurophilic interactions do play an essential role in bringing two porphyrin macrocycles exactly on top of each other with an unfavorable fully eclipsed geometry to produce short Hg···Hg distances. Interactions between Hg(II) dz2 orbitals provide the directionality with a linear Hg3 core having short Hg···Hg distances despite the fact that ligand framework is highly flexible.

Induction, control, and rationalization of supramolecular chirogenesis using metalloporphyrin tweezers: a structure-function correlation.

Supramolecular chirogenesis is one of the most rudimentary topics in the interdisciplinary sciences and essentially deals with various natural processes and innovative modern technologies. A comprehensive and rigorous understanding of such phenomenon is necessary to have a clear insight into the fundamental mechanisms and the various controlling factors, which would eventually lead to a range of practical applications of chiral supramolecular science. Metalloporphyrin tweezers have been extensively employed for such chirogenic processes due to their exciting physicochemical and tunable spectral properties, large stabilities, easily available synthetic protocols, and excellent abilities to form molecular assemblies. During the last few decades, various metalloporphyrin tweezers have been developed and considerably utilized by several research groups for assigning the absolute configuration to a variety of chiral diamines, conjugates of primary and secondary amines, amino alcohols, secondary alcohols, α-chiral carboxylic acids, etc. Our group has been at the forefront in trying to establish the structure-property correlation in this important area of interdisciplinary research. A brief account of our systematic investigation for understanding the underpinning mechanism of chirality induction and control at the molecular level over the last few years is presented in this Perspective article. The comprehensive understanding of such mechanistic details will be helpful in understanding various natural processes and designing modern technologies for various chirogenic functions in the fields of molecular sensors, nanotechnology, and supramolecular chemistry.