Allen J. Pistner

Synthesis, Electrochemistry, and Photophysics of a Family of Phlorin Macrocycles That Display Cooperative Fluoride Binding

A homologous set of 5,5-dimethylphlorin macrocycles in which the identity of one aryl ring is systematically varied has been prepared. These derivatives contain ancillary pentafluorophenyl (3H(Phl(F))), mesityl (3H(Phl(Mes))), 2,6-bismethoxyphenyl (3H(Phl(OMe))), 4-nitrophenyl (3H(Phl(NO2))), or 4-tert-butylcarboxyphenyl (3H(Phl(CO2tBu))) groups at the 15-meso-position. These porphyrinoids were prepared in good yields (35-50%) and display unusual multielectron redox and photochemical properties. Each phlorin can be oxidized up to three times at modest potentials and can be reduced twice. The electron-donating and electron-releasing properties of the ancillary aryl substituent attenuate the potentials of these redox events; phlorins containing electron-donating aryl groups are easier to oxidize and harder to reduce, while the opposite trend is observed for phlorins containing electron-withdrawing functionalities. Phlorin substitution also has a pronounced effect on the observed photophysics, as introduction of electron-releasing aryl groups on the periphery of the macrocycle is manifest in larger emission quantum yields and longer fluorescence lifetimes. Each phlorin displays an intriguing supramolecular chemistry and can bind 2 equiv of fluoride. This binding is allosteric in nature, and the strength of halide binding correlates with the ability of the phlorin to stabilize the buildup of charge. Moreover, fluoride binding to generate complexes of the form 3H(Phl(R))·2F(-) modulates the redox potentials of the parent phlorin. As such, titration of phlorin with a source of fluoride represents a facile method to tune the ability of this class of porphyrinoid to absorb light and engage in redox chemistry.

Factors Controlling the Spectroscopic Properties and Supramolecular Chemistry of an Electron Deficient 5,5-Dimethylphlorin Architecture.

A new 5,5-dimethylphlorin derivative (3H(PhlCF3)) was prepared and studied through a combination of redox, photophysical, and computational experiments. The phlorin macrocycle is significantly distorted from planarity compared to more traditional tetrapyrrole architectures and displays solvatochroism in the soret region of the UV–vis spectrum (∼370–420 nm). DFT calculations indicate that this solvatochromic behavior stems from the polarized nature of the frontier orbital (LUMO+1) that is most heavily involved in these transitions. Compound 3H(PhlCF3) also displays an intriguing supramolecular chemistry with certain anions; this phlorin can cooperatively hydrogen-bond two equivalents of fluoride to form 3H(PhlCF3)·2F– but does not bind larger halides such as Cl– or Br–. Analogous studies revealed that the phlorin can hydrogen-bond with carboxylate anions such as acetate to form 1:1 complexes such as 3H(PhlCF3)·OAc–. These supramolecular assemblies are robust and form even in relatively polar solvents such as MeCN. Hydrogen-bonding of fluoride and acetate anions to the phlorin N–H residues significantly attenuates the redox and photophysical properties of the phlorin. Moreover, The ability to independently vary the size and pKa of a series of carboxylate hydrogen-bond acceptors has allowed us to probe how phlorin–anion association is controlled by the anion’s size and/or basicity. These studies elucidate the physical properties and the electronic effects that shape the supramolecular chemistry displayed by the phlorin platform.

Electrochemical, Spectroscopic, and 1O2 Sensitization Characteristics of 10,10-Dimethylbiladiene Complexes of Zinc and Copper

The synthesis, electrochemistry, and photophysical characterization of a 10,10-dimethylbiladiene tetrapyrrole bearing ancillary pentafluorophenyl groups at the 5- and 15-meso positions (DMBil1) is presented. This nonmacrocyclic tetrapyrrole platform is robust and can serve as an excellent ligand scaffold for Zn2+ and Cu2+ centers. X-ray diffraction studies conducted for DMBil1 along with the corresponding Zn[DMBil1] and Cu[DMBil1] complexes show that this ligand scaffold binds a single metal ion within the tetrapyrrole core. Additionally, electrochemical experiments revealed that all three of the aforementioned compounds display an interesting redox chemistry as the DMBil1 framework can be both oxidized and reduced by two electrons. Spectroscopic and photophysical experiments carried out for DMBil1, Zn[DMBil1], and Cu[DMBil1] provide a basic picture of the electronic properties of these platforms. All three biladiene derivatives strongly absorb light in the visible region and are weakly emissive. The ability of these compounds to sensitize the formation of 1O2 at wavelengths longer than 500 nm was probed. Both the free base and Zn2+ 10,10-dimethylbiladiene architectures show modest efficiencies for 1O2 sensitization. The combination of structural, electrochemical, and photophysical data detailed herein provides a basis for the design of additional biladiene constructs for the activation of O2 and other small molecules.

Electrochemical, Spectroscopic, and 1O2 Sensitization Characteristics of Synthetically Accessible Linear Tetrapyrrole Complexes of Palladium and Platinum

The synthesis, electrochemistry, and photophysical characterization of a 10,10-dimethyl-5,15-bis(pentafluorophenyl)biladiene (DMBil1) linear tetrapyrrole supporting PdII or PtII centers is presented. Both of these nonmacrocyclic tetrapyrrole platforms are robust and easily prepared via modular routes. X-ray diffraction experiments reveal that the Pd[DMBil1] and Pt[DMBil1] complexes adopt similar structures and incorporate a single PdII and PtII center, respectively. Additionally, electrochemical experiments revealed that both Pd[DMBil1] and Pt[DMBil1] can undergo two discrete oxidation and reduction processes. Spectroscopic experiments carried out for Pd[DMBil1] and Pt[DMBil1] provide further understanding of the electronic structure of these systems. Both complexes strongly absorb light in the UV-visible region, especially in the 350-600 nm range. Both Pd[DMBil1] and Pt[DMBil1] are luminescent under a nitrogen atmosphere. Upon photoexcitation of Pd[DMBil1], two emission bands are observed; fluorescence is detected from ∼500-700 nm and phosphorescence from ∼700-875 nm. Photoexcitation of Pt[DMBil1] leads only to phosphorescence, presumably due to enhanced intersystem crossing imparted by the heavier PtII center. Phosphorescence from both complexes is quenched under air due to energy transfer from the excited triplet state to ground state oxygen. Accordingly, irradiation with light of λ ≥ 500 nm prompts Pd[DMBil1] and Pt[DMBil1] to photosensitize the generation of 1O2 (singlet oxygen) with impressive quantum yields of 80% and 78%, respectively. The synthetic accessibility of these complexes coupled with their ability to efficiently photosensitize 1O2 may make them attractive platforms for development of new agents for photodynamic therapy.

Stable Open-Shell Phosphorane Based on a Redox-Active Amidodiphenoxide Scaffold

The synthesis and redox reactivity of pentacoordinate phosphorus compounds incorporating a redox-active ONO amidodiphenoxide scaffold [ONO = N,N-bis(3,5-di-tert-butyl-2-phenoxide)amide] are described. Dichloro- and diphenylphosphoranes, 2·Cl2 and 2·Ph2, respectively, are synthesized and crystallographically characterized. Cyclic voltammograms of 2·Cl2 show only a single irreversible oxidation (Epa = +0.83 V vs Cp2Fe0/+), while the diphenyl analogue 2·Ph2 is reversibly oxidized at lower applied potential (E1/2 = +0.47 V vs Cp2Fe0/+). Chemical oxidation of 2·Ph2 with AgBF4 produces the corresponding radical cation [2·Ph2]•+, where electron paramagnetic resonance spectroscopy and density functional theory calculations reveal that the unpaired spin density is largely ligand-based and is highly delocalized throughout the ONO framework of the paramagnetic species. The solid-state structures indicate only minor geometrical changes between the neutral 2·Ph2 and oxidized [2·Ph2]•+ species, consistent with fast self-exchange electron transfer, as observed by NMR line-broadening experiments.