Roger Guilard

University of Burgundy | UB · Institut de Chimie Moléculaire de l'Université de Bourgogne (ICMUB)

Trisubstituted porphyrin derivatives [(TriMPyP)M][Formula: see text](Cl[Formula: see text] (where M = 2H, Zn[Formula: see text] or Pd[Formula: see text] containing three [Formula: see text]-methyl-4-pyridyl ([Formula: see text]-MePy[Formula: see text] groups were synthesized and characterized electrochemically and spectroscopically in DMSO containi...

New heterogeneous porous materials based on 5,10,15,20-(tetraphenyl)porphyrin (H 2 TPP), 5,10,15,20-(tetra-N-methyl-4-pyridyl)porphyrin tetrachloride (H 2 TNMPyP), zinc(II) 5,10,15,20-(tetra-N-methyl-4-pyridyl)porphyrin tetrachloride (ZnTNMP y P), 5,10,15,20-(tetra-4-carboxyphenyl)porphyrin (H 2 TCPP) and zinc(II)5,10,15,20-(tetra-4-carboxyphenyl)p...

Examples of photoluminescence (PL) are being reported with increasing frequency in a wide range of organisms from diverse ecosystems. However, the chemical basis of this PL remains poorly defined, and our understanding of its potential ecological function is still superficial. Among mammals, recent analyses have identified free-base por-phyrins as...

Spectacular photoluminescence (PL) phenomena have been increasingly reported in various organisms from diverse ecosystems. However, the chemical basis of this PL remains poorly defined, and its potential ecological function is still blurry, especially in mammals. Here we used state-of-the-art spectroscopy and multispectral imaging techniques to doc...

Spectacular photoluminescence (PL) phenomena have been increasingly reported in various organisms from diverse ecosystems. However, the chemical basis of this PL remains poorly defined, and its potential ecological function is still blurry, especially in mammals. Here we used state-of-the-art spectroscopy and multispectral imaging techniques to doc...

Examples of photoluminescence (PL) are being reported with increasing frequency in a wide range of organisms from diverse ecosystems. However, the chemical basis of this PL remains poorly defined, and our understanding of its potential ecological function is still superficial. Amongst mammals, recent analyses have identified free-base porphyrins as...

The derivatives of 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) are pivotal ingredients for a large number of functional, stimuli-responsive materials and therapeutic molecules based on their photophysical properties, and there is a urgent need to understand and predict their optical traits prior to investing a large amount of resources in p...

Photodynamic Inactivation is an innovative technique used to combat bacterial and viral infections which involves the use of photosensitizing agents along with light to generate cytotoxic reactive oxygen species able to kill bacteria and viruses. In the first section of this minireview, porphyrin-based fluorophores are shown to be remarkable dye ca...

Water-soluble cationic porphyrins have been shown to possess promising therapeutic potential, through biochemical processes. which depend on solubility as well as the extent of aggregation. under biological conditions. These properties are influenced by a multitude of factors the most important of which are the number of positively charged meso-sub...

Three series of porphyrins containing a Zn(II) central metal ion and zero, one, or two phosphoryl groups at the meso-positions of the macrocycle were characterized as to their electrochemical, spectroscopic, and structural properties in nonaqueous media. The investigated compounds are represented as 5,15-bis(4′-R-phenyl)porphyrinatozinc, 10-(dietho...

Photodynamic therapy is an innovative approach to treat diverse cancers and diseases that involves the use of photosensitizing agents along with light of an appropriate wavelength to generate cytotoxic reactive oxygen species. Among the collection of potential dye candidates, porphyrinoids (i.e. porphyrins, chlorins, and phthalocyanines) are probab...

The synthesis and structural characterization, both in solution by means of (1)H and (31)P NMR and UV-vis spectroscopies and in the solid state by X-ray diffraction on single crystal, of a series of gallium(III) and indium(III) meso-mono(diethoxyphosphoryl)porphyrins bearing different peripheral substituents as well as the corresponding monoesters...

Dyad 4, composed of cofacial free-base porphyrins (acceptor), [Fb]2 bridged by a 1,4-C6H4 group to a free-base antenna (donor), [Fb] is investigated for singlet energy transfer thus completing a series of investigations into similar structures that contained [Mg]2 and [Zn]2 cofacial units. The previously reported [Mg]2 and [Zn]2 based dyads exhibit...

Functional properties of porphyrins are widely exploited in natural and artificial systems. The molecular structure of free base porphyrins and their complexes can be precisely adapted to the target function and the operating environment by varying the substituents on the macrocycle and the metal centres. Another tool widely used by nature to incre...

Green Chemistry has evolved in response to several environmental issues in the second half of the last century, mostly due to the almost freely expanding chemical, petrochemical, and pharmaceutical industries. During the past two decades Green Chemistry grew rapidly and we can now consider this area as a mature and powerful field. Tremendous develo...

A two-step reaction sequence for accessing meso-(dialkoxyphosphoryl)porphyrins from readily available trans-A2-type porphyrins was developed. This approach involves bromination and subsequent palladium-catalyzed phosphonylation. Optimal conditions for both steps were identified after exploration of various reaction parameters such as solvent, tempe...

The reaction of phosphorylated 1,10-phenanthrolines 3-Pphen, 3,8-Pphen and 4,7-Pphen (3-Pphen = 3-diethoxyphosphorylphenanthroline, 3,8-Pphen = 3,8-bis(diethoxyphosphoryl)phenanthroline, 4,7-Pphen = 4,7-bis(diethoxyphosphoryl)phenanthroline) and hydrated copper(ii) nitrate in a 1:1 ratio leads to the formation of supramolecular architectures. In th...

An innovative design of reusable SPR chips allowing the quantitative and selective determination of mercury(II) at ppt level is reported.

The synthesis of functionalized porphyrins and conjugates from meso-tetraarylporphyrins through the acylation and the oxidation of β-aminoporphyrins was investigated. 2,3-Dioxochlorins were prepared by the oxidation of a variety of β-aminoporphyrins and subsequently used in a condensation reaction with functionalized aromatic aldehydes and ammonium...

meso-RO-appended (R = alkyl, aryl) porphyrins bearing one or two OR substituents at the tetrapyrrolic macrocycle were synthesized in good yields from 5,15-dibromo-10,20-diphenylporphyrins 2H(Br2DPP), Ni(Br2DPP) and Zn(Br2DPP) using an SNAr reaction. By varying the solvent, the base, the temperature, and the time of the reaction, the optimum conditi...

A new paradigm is described that allows one to create different types of sensors: from highly sensitive ones to practical household devices. Our approach relies on modular molecular receptors incorporating an intensely-colored aminoanthraquinone signaling unit equipped with both hydrophilic and hydrophobic modules, the number and size of which bein...

Two series of diphosphoryl-substituted porphyrins were synthesized and characterized by electrochemistry and spectroelectrochemistry in benzontrile, dichloromethane and pyridine containing 0.1 M tetra- n -butylammonium perchlorate. The investigated compounds are represented as 5,15-bis(diethoxyphosphoryl)-10,20-diphenylporphyrins and 5,15-bis-(diet...

Two series of diphosphoryl-substituted porphyrins were synthesized and characterized by electrochemistry and spectroelectrochemistry in nonaqueous media containing 0.1 M tetra-n-butylammonium perchlorate (TBAP). The investigated compounds are 5,15-bis(diethoxyphosphoryl)-10,20-diphenylporphyrins (Ph)2(P(O)(OEt)2)2PorM and 5,15-bis(diethoxyphosphory...

The present invention relates to a material notably adapted for the extraction of metal cations in an aqueous medium, comprising a solid support on which are attached polyazacycloalkane compounds having a ring including at least 4 nitrogen atoms, and wherein the nitrogen atoms of the ring are substituted with coordinating groups, which each are ind...

N,N',N '',N'''-Tetrabenzyl derivatives of cyclen and cyclam possessing two bromine atoms in trans-positioned phenyl rings were introduced in the Pd-catalyzed amination reactions with oxadiamines and polyamines to provide a wide series of macrobicyclic compounds with tetrabenzyl substituted cyclen and cyclam central moieties in yields up to 31%. Mac...

Thiopheno[[]b]mono and bishomotropones are readily synthesized from thiopheno[[]b]tropones and dimethyloxosulfonium methylide. The position, the nature of the seven-membered ring substituents, and the reaction medium are the most important parameters of the cyclopropanation reaction. The structure of the monohomotropones is established by compariso...

doi: 10.1080/10426507.2014.985823

Porphyrins are an important family of organic chromophores that have attracted attention as photosensitizers in TiO2 -based dye-sensitized solar cells (DSSCs). This brief review is dedicated to comparative studies of phosphonic and carboxylic acid anchoring groups for attachment of porphyrin sensitizers on semiconductors or conductors surface. Here...

The reactions of dicopper tetrapivalate complex Cu2(μ-OOC-t-Bu)4(NCMe)2 (1) with triphenylphosphine oxide and diethyl phosphite allow paddle-wheel (PW) copper(II) complexes with phosphorus-containing axial ligands (2, 3) to be obtained. When meso-bis(diethoxyphosphoryl)porphyrins 4M were employed in this ligand exchange reaction, a series of one-di...

Material composed of a polyazacycloalkane grafted on polypropylene fibres. Process for the preparation of this material. Process for removing metal cations present in a liquid by bringing this liquid into contact with the said material.

Several metal complexes of 5,15-bis(diethoxyphosphoryl)-10,20-diphenylporphyrin 1M (M = Cd(II), Ni(II), Pd(II), Pt(II)) were synthesized and crystallographycally characterized. Crystal organization patterns were analyzed using DFT (B97-D3/def2-SVP) calculations of intermolecular interaction energies between complexes in the crystals. For the system...

Two series of copper(I) complexes with diethoxyphosphoryl-substituted 1,10-phenanthroline ligands were synthesized and characterized in the solid state and in solution. The first comprised mixed-ligand CuI complexes with phenanthroline and triphenylphosphine. The second series includes bis-chelates with two phenanthroline ligands. According to the...

This brief review summarizes the synthetic approaches towards porphyrins bearing a C-P bond at the periphery of the macrocycle. In the first section we detail the non catalytic pathways for the synthesis of phosphorus substituted porphyrins using different phosphonate precursors or by derivatization of a pre-existing porphyrin. In the second sectio...

Suzuki–Miyaura cross-coupling reaction has been used for the synthesis of tricyclic architectures based on trans-A2B2-porphyrins and bisaminal-protected polyazamacrocycles which are linked directly or by a p-phenylene spacer. This modular approach allowed the synthesis of ligands with various substituted porphyrin macrocycles and bisaminal-protecte...

The review covers an important area of the modern chemistry, namely, the detection of heavy metal ions using optical molecular detectors. The role of this method in metal ion detection and the physicochemical grounds of operation of chemosensors are discussed, and examples of detection of most abundant heavy metal ions and synthetic approaches to m...

A series of 2-aryl-substituted 1-aminocyclopropylphosphonates containing an additional remote phosphonate group have been synthesized starting from readily accessible dimethyl (1R∗,2R∗)-2-(4-bromophenyl)-1-formamidocyclopropylphosphonate using cross-coupling methodology. Different types of palladium-catalyzed reactions for carbon-carbon and carbon-...

A pentaazamacrocycle incorporating an intracyclic anthraquinone fragment (PENTAQ) was synthesized with the aim of forming metal-responsive Langmuir monolayers. PENTAQ allows a good discrimination by naked eye of copper ions in methanol/water solutions (50:50 v/v). Spectrophotometric investigations of the protonation and Cu2+ binding properties of P...

Pd-catalyzed amination reactions were employed for the synthesis of macrobicyclic compounds possessing cyclen or cyclam moieties, naphthylmethyl spacers and polyamine linkers. The results of the macrocyclization reactions involving 1,7-bis(4-bromonaphthyl-1-methyl) cyclen and 1,8-bis(4-bromonaphthyl-1-methyl) cyclam were shown to be dependent on th...

Synthesis of trismacrocyclic compounds with a central tetraazamacrocyclic moiety and two aza-crown ether fragments was carried out using the Pd-catalyzed amination of trans-bis(bromobenzyl) substituted cyclen and cyclam with 3 equiv. of azacrown ethers. The yields were shown to be dependent on the nature of the starting tetraazamacrocycles and reac...

The electrochemical and spectroelectrochemical properties of two β-phosphorylated Zn porphyrins, [2-diethoxyphosphoryl-5,10,15,20-tetraphenylporphyrinato]zinc (1) and [2-diisopropoxyphosphoryl-5,10,15,20-tetraphenylporphyrinato]zinc (2), are reported in CH2Cl2 and PhCN containing tetrabutylammonium perchlorate (TBAP) or tetrabutylammonium hexafluor...

A dyad, 1, built on an artificial special pair (bis(meso-nonyl)zinc(II)porphyrin), [Zn2], a spacer (biphenylene), a bridge (1,4-benzene), and an antenna (di-meso-(3,5-di(t-butyl)phenyl)porphyrin free base), FB, is prepared by Suzuki coupling and is analyzed by absorption and steady state, and time-resolved emission spectroscopy at 298 and 77 K. Usi...

Using a selective stepwise Suzuki cross-coupling reaction, two trimers built on three different chromophores were prepared. These trimers exhibit a D(∧)A1-A2 structure where the donor D (octa-β-alkyl zinc(II)porphyrin either as diethylhexamethyl, 10a, or tetraethyltetramethyl, 10b, derivatives) through space transfers the S1 energy to two different...

Reactions of aromatic amines with 3,3′-bithiophene-2,2′-dicarbaldehyde 1 and 3,3′-bithiophene-4,4′-dicarbaldehyde 2 gave the 2,2′-(N-(aryl)diimino)-3,3′-bithiophene 3 and 4,4′-(N-(aryl)diimino)-3,3′-bithiophene 4 in good yields. Orthophenylenediamine reacted with 1 and 2 to give dithieno[3,4-c;4′,3′-e]azepino[1,2-a]benzimidazole 5 and dithieno[2,3-...

The photosynthetic membranes in plants and photosynthetic bacteria, such as the purple photosynthetic bacteria, exhibit a reaction center protein that contains a special pair built on a cofacial slipped dimer of chlorophylls or bacteriochlorophylls. This reaction center is surrounded by antennas that serve to absorb light and funnel this excitation...

A cofacial bis(Mg(ii)porphyrin)-C(6)H(4)-free base ([Mg(2)]-bridge-FB) dyad shows S(1) energy transfer in both directions and much slower rates than similar monoporphyrin systems are observed.

A new colorimetric molecular sensor allowing for cheap, fast, sensitive, and highly selective naked-eye detection of Hg(2+) in water is described. This molecule combines a 1,8-diaminoanthraquinone signaling subunit and phosphonic acid esters that confer the water solubility to the dye (R = H). A ready-to-use colorimetric solid sensor was obtained b...

Copper(II) 5,15-bis(diethoxyphosphoryl)-10,20-diphenylporphyrin was obtained and characterized by means of cyclic voltammetry, electron paramagnetic resonance, Fourier transform infrared, and UV-visible spectroscopy. Three crystalline forms were grown and studied by means of X-ray diffraction methods (single crystal and powder). The highly electron...

Two approaches were elaborated for the synthesis of macrocycles comprising two naphthalene and two polyamine moieties (cyclodimers). The first one includes the synthesis of N,N'-bis(7-bromonaphth-2-yl) substituted polyamines via Pd-catalyzed amination reaction of polyamine with excess of 2,7-dibromonaphthalene, followed by the Pd-catalyzed macrocyc...

This review presents the synthetic approach for the design of tris(macrocycles) as bio-inspired models for light harvesting devices in plants and photosynthetic bacteria based on cofacial bisporphyrins and a porphyrin unit attached as a side arm. Two types of tris(porphyrins) are described herein depending on the nature of the chromophores of the c...

Palladium-catalyzed amination was successfully applied to the synthesis of macrobicyclic cryptands comprising cyclen or cyclam and pyridine moieties. Starting bis(halopyridylmethyl) substituted cyclen and cyclam were obtained from protected tetraazamacrocycles in good yields and introduced in the catalytic macrocyclization reactions with a number o...

Series of 5-bromo-15-R-10,20-diphenylporphyrins 1a-d, 2a-g (where R = CN, COOMe, Br, H, morpholinyl, NH2, PrNH, tBuNH, Pr2N, PhNH, Ph2N) is investigated by means of density functional theory (DFT) in order to reveal their reactivity towards the nucleophilic substitution reaction. The influence of the electronic effects of the 15-substituent on the...

The Porphyrin Handbook, Volume 18: Multiporphyrins, Multiphthalocyanines and Arrays provides information pertinent to every aspect of the chemistry, synthesis, spectroscopy, and structure of phthalocyanines. This book examines the biology and medical implications of porphyrin systems. Organized into five chapters, this volume begins with an overvie...

The first synthesis and self-organization of zinc β-phosphorylporphyrins in the solid state and in solution are reported. β-Dialkoxyphosphoryl-5,10,15,20-tetraphenylporphyrins and their Zn(II) complexes have been synthesized in good yields by using Pd- and Cu-mediated carbon-phosphorous bond-forming reactions. The Cu-mediated reaction allowed to pr...

A general protocol for the coupling of mono- and dihalo-1,10-phenanthrolines with di-Et phosphite is reported. This reaction proceeds smoothly in the presence of a Pd(OAc)2/dppf catalytic system and triethylamine as a base.

Bis(bromobenzyl)derivatives of cyclen and cyclam obtained according to previously described procedures were introduced in a palladium-catalyzed reaction with 1,3-bis(aminomethyl)adamantane and 1,3-bis(2-aminoethyl)adamantane to produce macrobicycles in moderate yields. The formation of tricyclic cyclodimers was observed in many cases. Tetrabenzyl d...

Trimer 2, composed of a cofacial heterobismacrocycle, octamethyl-porphyrin zinc(II) and bisarylporphyrin zinc(II) held by an anthracenyl spacer, and a flanking acceptor, bisarylporphyrin free-base (Ar = -3,5-(tBu)2C6H3), has been studied by means of absorption spectroscopy, "steady state and time-resolved fluorescence" and fs transient absorption s...

A pi-extended viologen has been synthesized, forming supramolecular complexes with a freebase tetraphenylporphyrin (H2TPP) and the cofacial porphyrin dimer with an anthracene spacer [H-4(DPA)] through pi-pi interaction in benzonitrile (PhCN). Formation of the H2TPP-BHV2+ supramolecular complex was probed by UV-vis and fluorescence spectra. The fluo...

Three approaches to three types of cyclen-based macrotricycles have been elaborated starting from trans-bis(3-bromobenzyl)cyclen. The macrotricycles were synthesized via Pd-catalyzed amination. The first approach employed consecutive macrocyclization and benzylation steps giving a cage-like tricycle. In the second, cyclen amino groups were Boc-prot...

The Porphyrin Handbook, Volume 11: Bioinorganic and Bioorganic Chemistry presents the fundamental aspects of the synthesis, structure, chemistry, and spectroscopy of phthalocyanines. This book discusses the biology and medical implications of porphyrin systems. Organized into seven chapters, this volume begins with an overview of the design, synthe...

The Porphyrin Handbook, Volume 18: Multiporphyrins, Multiphthalocyanines and Arrays provides information pertinent to every aspect of the chemistry, synthesis, spectroscopy, and structure of phthalocyanines. This book examines the biology and medical implications of porphyrin systems. Organized into five chapters, this volume begins with an overvie...

The Porphyrin Handbook, Volume 15: Phthalocyanines: Synthesis provides information pertinent to every aspect of the chemistry, synthesis, spectroscopy, and structure of phthalocyanines. This book examines the biology and medical implications of porphyrin systems. Organized into five chapters, this volume begins with an overview of the importance of...

The Porphyrin Handbook, Volume 14: Medical Aspects of Porphyrins provides information pertinent to every aspect of the chemistry, synthesis, spectroscopy, and structure of phthalocyanines. This book examines the biology and medical implications of porphyrin systems. Organized into 12 chapters, this volume begins with an overview of the underlying d...

The Porphyrin Handbook, Volume 12: The Iron and Cobalt Pigments: Biosynthesis, Structure, and Degradation provides information pertinent to every aspect of the chemistry, synthesis, spectroscopy, and structure of phthalocyanines. This book presents the biochemical and clinical aspects of genetically transmitted or drug-induced diseases associated w...

The Porphyrin Handbook, Volume 20: Phthalocyanines: Structural Characterization provides information pertinent to every aspect of the chemistry, synthesis, spectroscopy, and structure of phthalocyanines. This book examines the biology and medical implications of porphyrin systems. Organized into one chapter, this volume begins with an overview of t...

The Porphyrin Handbook, Volume 16: Phthalocyanines: Spectroscopic and Electrochemical Characterization provides information pertinent to every aspect of the chemistry, synthesis, spectroscopy, and structure of phthalocyanines. This book examines the biology and medical implications of porphyrin systems. Organized into five chapters, this volume beg...

The Porphyrin Handbook, Volume 13: Chlorophylls and Bilins: Biosynthesis, Synthesis, and Degradation provides information pertinent to every aspect of the chemistry, synthesis, spectroscopy, and structure of phthalocyanines. This book examines the biology and medical implications of porphyrin systems. Organized into eight chapters, this volume begi...

X-ray Detected Magnetic Resonance (XDMR) is a novel spectroscopy in which X-ray Magnetic Circular Dichroism (XMCD) is used to probe the resonant precession of local magnetization components in a strong microwave pump field. We review the conceptual bases of XDMR and recast them in the general framework of the linear and nonlinear theories of ferrom...

This review presents the synthetic aspects and photophysical properties of trimeric systems constructed with a first unit consisting of a cofacial porphyrin and then of another porphyrin attached as a side arm. Two scenarios are dealt with. The first one is the case where the three chromophores are different, called donor 1–donor 2–acceptor, specif...

The singlet k(ET) for cofacial β-octaalkylporphyrin/bis(meso-aryl)porphyrin dyads increases linearly with the gap between the donor-acceptor 0-0 fluorescence peaks at 77 K.

A family of water-soluble colorimetric chemosensors incorporating an anthraquinone signalling subunit functionalized with a polyamine chain that bears hydrophilic diethoxyphosphoryl moieties was prepared with the aim of assaying metal cations. The outstanding UV-Vis absorption properties of the 1-aminoanthraquinone chromophore allowed the efficient...

In this work, three new cyclam-based ligands L1, L2 and L3 bearing N-sulfonylacetamide pendant arm and their Cu(II), Zn(II), Cd(II) and Pb(II) complexes were synthesized and characterized by mass spectrometry, NMR, infrared and UV-Vis spectroscopies. The ligands present an original zwitterionic form in which the nitrogen atom of the sulfonylacetami...

Metal-organic frameworks constructed by self-assembly of metal ions and organic linkers have recently been of great interest in the preparation of porous hybrid materials with a wide variety of functions. Despite much research in this area and the large choice of building blocks used to fine-tune pore size and structure, it remains a challenge to s...

The synthesis and electrochemical characterization of two related series of porphyrins bearing diethoxyphosphoryl groups are reported. One group of compounds is represented as (T(p-R)PP)M where R=phos=P(O)(OEt)2 and M=Zn(II) or H2 while the other is represented as (di(p-R)Pdi(phos)P)M where R=P(O)(OEt)2, H or CH3 and M=Zn(II) or H2. Each porphyrin...