Mathias O. Senge

Trinity College Dublin | TCD · School of Chemistry

Heavy atom-free BODIPY-anthracene dyads (BADs) upon photoexcitation generate locally excited triplet excited states by way of photoinduced electron transfer (PeT), followed by recombination of the resulting charge-separated states (CSS). Subsequent quenching of the triplet states by molecular oxygen produces singlet oxygen (1O2), which reacts with...

For the first time, free base and N-methylated porphyrins have been utilized as bifunctional organocatalysts in Michael additions and it was found that distortion of the macrocycle is a vital prerequisite for their catalytic activity. Conformational design has been used to tailor the properties of nonplanar porphyrins with regards to availability o...

The selectivity and functional variability of porphyrin cofactors are typically based on substrate binding of metalloporphyrins wherein the pyrrole nitrogen units only serve to chelate the metal ions. Yet, using the porphyrin inner core system for other functions is possible through conformational engineering. As a first step towards porphyrin “enz...

Porphyrins feature prominently in nature, be it as enzymatic cofactors, electron and exciton shuffles, as photoactive dyes, or as signaling substances. Their involvement in the generation, storage and use of oxygen is pivotal to life, while their photochemical properties are central to the biochemical functioning of plants. When complexed to metals...

We report a two‐step approach to obtain synthetically versatile bicyclo[1.1.1]pentane (BCP) derivatives using Grignard reagents. This method allows the incorporation of BCP units in tetrapyrrolic macrocycles and the synthesis of a new class of calix[4]pyrrole analogues by replacing two bridging methylene groups with two BCP units. In addition, a do...

Unlike their planar counterparts, classic synthetic protocols for C–C bond forming reactions on nonplanar porphyrins are underdeveloped. The development of C–C bond forming reactions on nonplanar porphyrins is critical in advancing this field of study for more complex porphyrin architectures, which could be used in supramolecular assemblies, cataly...

A supramolecular approach based on self-assembled structures allows the formation of large structured co-assemblies based on chiral and achiral compounds with original physicochemical features. In this contribution, an achiral and...

We imagine molecules to be perfect, but rigidified units can be designed to bend from their ideal shape, discarding their symmetric elements as they progress through vibrations and larger, more permanent distortions. The shape of molecules is either simulated or measured by crystallography and strongly affects chemical properties but, beyond an ima...

Porphyrin atropisomerism, which arises from restricted σ‐bond rotation between the macrocycle and a sufficiently bulky substituent, was identified in 1969 by Gottwald and Ullman in 5,10,15,20‐tetrakis(o‐hydroxyphenyl)porphyrins. Henceforth, an entirely new field has emerged utilizing this transformative tool. This review strives to explain the cons...

Controlling spectral properties to achieve desired characteristics is an attractive goal in application-oriented research, e.g., in the design of fluorescence sensors. “Soft” chromophores, molecules with strong spectral responses to internal...

Symmetry and shape are essential aspects of molecular structure and how we interpret molecules and their properties. We, as chemists, are comfortable with pictorial representations of structure, in which some nuance is lost—investigating molecular shape numerically by looking at how closely it fits a reference, such as a plane, or a set of vectors...

Symmetry and shape are essential aspects of molecular structure and how we interpret molecules and their properties. We, as chemists, are comfortable with pictorial representations of structure, in which some nuance is lost – investigating molecular shape numerically by looking at how closely it fits a reference, such as a plane, or a set of vector...

Tuberculosis (TB) is a global pandemic killing millions of people every year. Yet, resistant strains make curing TB quite challenging. Herein, a series of new pyrazole-linked benzothiazole hybrids was synthesized and evaluated for their anti-TB activity against three Mycobacterium tuberculosis strains (drug sensitive (DS), multidrug-resistant (MDR)...

Unter anderem das hat die Organik im letzten Jahr bewegt: milde Oxidation mit Elektrochemie, Oxidation zu enantiomerenreinen Sulfonylverbindungen, Flüssigkristallphasen erkennen mit maschinellem Lernen, CO 2 reagiert zu Succinat und Carbamaten, eine Alternative zu Bisphenol A, Subporphyrine, photoschaltbare Spinmaterialien, photochemische Thiophen‐...

We imagine molecules to be perfect, but rigidified units can be designed to bend from their ideal shape, discarding their symmetric elements as they process through vibrations and larger, more permanent distortions. The shape of molecules is either simulated or measured by crystallography and strongly affects chemical properties but, beyond an imag...

Porphyrin-based metal–organic frameworks (MOFs) are attractive materials for photo- and thermally activated catalysis due to their unique structural features related to the porphyrin moiety, guest-accessible porosity, and high chemical tunability. In this study, we report the synthetic incorporation of nonplanar β-ethyl-functionalized porphyrin lin...

Photodynamic therapy (PDT) is an anticancer therapy with proven efficacy; however, its application is often limited by prolonged skin photosensitivity and solubility issues associated with the phototherapeutic agents. Injectable hydrogels which can effectively provide intratumoral delivery of photosensitizers with sustained release are attracting i...

A chitosan-based hydrogel that enables sustained and controlled delivery of a temoporfin derivative, which permits multiple irradiations after a single intratumoral administration. This strategy combines efficient cell killing with antitumor immunity. Biomacromolecules 2024, 25, 1, 24–42

In the development of two‐qubit quantum gates, precise control over the intramolecular spin‐spin interaction between molecular spin units plays a pivotal role. A weak but measurable exchange coupling is especially important for achieving selective spin addressability that allows controlled manipulation of the computational basis states ǀ00⟩ ǀ01⟩ ǀ1...

In the development of two‐qubit quantum gates, precise control over the intramolecular spin‐spin interaction between molecular spin units plays a pivotal role. A weak but measurable exchange coupling is especially important for achieving selective spin addressability that allows controlled manipulation of the computational basis states |00⟩ |01⟩ |1...

Aromaticity is an established and widely used concept for the prediction of the reactivity of organic molecules. However, its role remains largely unexplored in on-surface chemistry, where the interaction with the substrate can alter the electronic and geometric structure of the adsorbates. Here we investigate how aromaticity affects the reactivity...

(Front Cover) Supramolecular Chirogenesis in a Sterically Hindered Porphyrin: A Critical Theoretical Analysis

Invited for the cover of this issue are the groups of Irina Osadchuk at Tallinn University of Technology and Mathias Senge at Trinity College Dublin. The image depicts how a porphyrin with two guest molecules (R)‐camphor sulfonic acid is irradiated with UV‐visible light to measure and simulate ECD and UV‐Vis spectra. Read the full text of the artic...

The determination of molecular stereochemistry and absolute configuration is an important part of modern chemistry, pharmacology, and biology. Electronic circular dichroism (ECD) spectroscopy is a widely used tool for chirality assignment, especially with porphyrin macrocycles employed as reporter chromophores. However, the mechanisms of induced EC...

The crystal structure of (R,R)-4-bromo-2-{4-[4-bromo-1-(4-toluene­sulfon­yl)-1H-pyrrol-2-yl]-1,3-di­nitro­butan-2-yl}-1-(4-toluene­sulfon­yl)-1H-pyrrole (1, C26H24Br2N4O8S2) is presented. The title compound was isolated in suitable yield as a by-product in our synthesis of geminal-dimethyl hydro­dipyrrins. We observe an unforeseen enanti­omeric res...

Bicyclo[1.1.1]pentane (BCP) motifs are of growing importance to the pharmaceutical industry as sp3‐rich bioisosteres of benzene rings and as molecular tectons in materials science. Herein we explore the behavior of 1,3‐disubstituted BCP moieties on metal surfaces by combining low‐temperature scanning tunneling microscopy / non‐contact atomic force...

The determination of molecular stereochemistry and absolute configuration is an important part of modern chemistry, pharmacology, and biology. Electronic circular dichroism (ECD) spectroscopy is a wildly used tool for chirality assignment, especially with porphyrin macrocycles employed as reporter chromophores. However, the mechanisms of induced EC...

This review follows the research, development and clinical applications of the photosensitizer 5,10,15,20‐tetra(m‐hydroxyphenyl)chlorin (mTHPC, temoporfin) in photodynamic (cancer) therapy (PDT) and other medical applications. Temoporfin is the active substance in the medicinal product Foscan® authorized in the EU for the palliative treatment of he...

Bicyclo[1.1.1]pentane (BCP) motifs are of growing importance to the pharmaceutical industry as sp³‐rich bioisosteres of benzene rings and as molecular building blocks in materials science. Herein we explore the behavior of 1,3‐disubstituted BCP moieties on metal surfaces by combining low‐temperature scanning tunneling microscopy / non‐contact atomi...

We report a two‐step approach to obtain synthetically versatile bicyclo[1.1.1]pentane (BCP) derivatives using Grignard reagents. This method allows the incorporation of BCP units in tetrapyrrolic macrocycles and the synthesis of a new class of calix[4]pyrrole analogues by replacing two bridging methylene groups with two BCP units. In addition, a do...

Polystyrolproben werden mit Eisen(III)chlorid und weißen LEDs zu Oligomeren und Benzoylprodukten; ein Wolframatkatalysator invertiert die Absolutkonfiguration an sp3‐Kohlenstoffzentren; gelöstes Rätsel um eine symmetrieverbotene konrotatorische 14‐Elektronen‐Elektrocyclisierung; Polycarbonate, die sich ohne Lösungsmittel recyceln lassen: Highlights...

We report a two-step approach to obtain synthetically versatile bicyclo[1.1.1]pentane (BCP) derivatives using Grignard reagents. This method allows the incorporation of BCP units in tetrapyrrolic macrocycles and the synthesis of a new class of calix[4]pyrrole analogues by replacing two bridging methylene groups with two BCP units. In addition, a do...

The crystal structures of three S-(pyridin-2-yl) benzo­thio­esters with varying para-phenyl substituents are presented, namely, S-(pyridin-2-yl) 4-nitro­benzo­thio­ate (1, C12H8N2O3S), S-(pyridin-2-yl) 4-methyl­benzo­thio­ate (2, C13H11NO2S) and S-(pyridin-2-yl) 4-meth­oxy­benzo­thio­ate (3, C13H11NO2S). This class of compounds are used in the mono...

The time dependence of atropisomer interconversion has limited the pursuit of single atropisomer drug candidates, even in circumstances where one atropisomer presents favorable biological activity over another. Moderate interconversion energy barriers risk compromising drug stability. As a result, examples of atropisomerically pure drugs in current...

Photodynamic therapy (PDT) is an anti-cancer therapy with proven efficacy; however, its application is often limited by prolonged skin photosensitivity and solubility issues associated with the phototherapeutic agents. Injectable hydrogels that can effectively provide intra-tumoral delivery of photosensitizers with sustained release is attracting i...

The growing demand for energy and the excessive use of fossil fuels represents one of the main challenges for humanity. Storing solar energy in the form of chemical bonds to generate solar fuels or value-added chemicals without creating additional environmental burdens is a key requirement for a sustainable future. Here we use biomimetic artificial...

Coordinating the spatial arrangement of electroactive partners is crucial to designable molecular electronics and photonics. Porphyrins are ubiquitous reaction centers in nature; synthetic porphyrins, in the crystallographic solid state, are often coerced into monolithic stacks, inhibiting reactivity. Using the principles of self-organization, and...

Within this work, we review the metal coordination effect on the photophysics of metal dipyrrinato complexes. Dipyrrinato complexes are promising candidates in the search for alternative transition metal photosensitizers for application in photodynamic therapy (PDT). These complexes can be activated by irradiation with light of a specific wavelengt...

Within this work we review the metal coordination effect on the photophysics of metal dipyrrinato complexes. Dipyrrinato complexes are promising candidates in the search for alternative transition metal photosensitizers for application in photodynamic therapy (PDT). These complexes can be activated by irradiation with light of a specific wavelength...

Porphyrins are variously substituted tetrapyrrolic macrocycles, with wide-ranging biological and chemical applications derived from metal chelation in the core and the 18π aromatic surface. Under suitable conditions, the porphyrin framework can deform significantly from regular planar shape, owing to steric overload on the porphyrin periphery or st...

The intrinsic challenge of large molecules to cross the cell membrane and reach intracellular targets is a major obstacle for the development of new medicines. We report how rotation along a single C–C bond, between separable atropisomers, of a drug in clinical trials improves cell uptake and therapeutic efficacy. The atropisomers of redaporfin (a...

5,10,15,20-Tetrakis(3-hydroxyphenyl)porphyrin (m-THPP) bearing various nitrogen and sulfur containing heterocycles, aromatic, aliphatic and alicyclic residues covalently linked to the oxygen atom of the meta-hydroxy group of the porphyrin unit were synthesized in good yields as potential photosensitizers for photodynamic therapy (PDT). These new am...

Two graphene oxide nanoassemblies using 5-(4-(aminophenyl)-10,15,20-triphenylporphyrin (TPPNH2) were fabricated by two synthetic methods: covalent (GO-CONHTPP) and noncovalent bonding. GO-CONHTPP was achieved through amide formation at the periphery of GO sheets and the hybrid material was fully characterized by FTIR, XPS, Raman spectroscopy, and S...

The number of drug-resistant bacteria is increasing significantly. To combat such issues, antimicrobial PDT (aPDT) provides an efficient way to eliminate these species efficiently, cost-effectively, and more importantly, without the associated mechanism of resistance. The hemisynthesis and synthesis of photosensitizers such as polyaminated chlorin-...

Porphyrin is the ligand that encapsulates iron in heme, the active site of the red blood cell protein hemoglobin. In plants, porphyrins in the form of magnesium complexes are the key players in photosynthesis. Porphyrin colors are also encountered in daily life. Many colors around us are related to porphyrin biosynthesis and catabolism. The early d...

The chapter reviews past and current ways of naming and classifying synthetic and natural porphyrinoids and covers the older Fischer and modern IUPAC‐IUB nomenclature. The latter provides a convenient system of naming standard porphyrin derivatives, but has not kept pace with the explosive development of new classes of porphyrins with altered macro...

The synthesis and functionalization of porphyrins is a long‐established but still burgeoning field. It has seen many advances, from studies on the fundamental natural heme and chlorophyll systems, to an ever‐expanding array of complex tetrapyrroles that are used in a multitude of modern applications ranging from biochemistry to catalysis, medicine...

BODIPYs have been extensively used for biological imaging owing to their high fluorescent quantum yields of stability toward photobleaching. In this work, zwitterionic groups were introduced into trimethoxyphenyl-BODIPY derivatives to improve their water-solubility. The impact of the substitution pattern of the methoxy groups in the phenyl motif an...

Recently prochiral solvating agents (pro-CSA) became a spotlight for the detection of enantiopurity by NMR. Chemical shift non-equivalency in achiral hosts introduced by the presence of chiral guests yields observable resonance signal splitting (Δδ) correlating to the enantiomeric excess (e.e.). In this work, symmetry is our lens to explain porphyr...

Photodynamic therapy (PDT) is a multi-component therapy which relies on the delivery of a photosensitizer drug and light in the presence of oxygen to mediate a therapeutic anti-cancer or anti-microbial effect. As a multi-component therapy, a multidisciplinary research approach is required to achieve success with the application of PDT. The POLYTHEA...

Free base 5,10,15,20-tetrakis(4-carboxylatophenyl)porphyrin stands for the class of powerful porphyrin photosensitizers for singlet oxygen generation and light-harvesting. The atomic level selectivity of dynamic UV pump - N K-edge probe X-ray absorption spectroscopy in combination with time-dependent density functional theory (TD-DFT) gives direct...

Flüssigkristalle als responsive Materialien etwa in der organischen Elektronik, erste Nanogürtel mit Acencharakter, direkt aus der Atmosphäre entferntes CO2, Disauerstoff wird organokatalytisch zu Wasserstoffperoxid, und Chinazolinone lassen sich biokatalytisch herstellen.

Recently prochiral solvating agents (pro-CSA) became a spotlight for the detection of enantiopurity by NMR. Chemical shift non-equivalency in achiral hosts introduced by the presence of chiral guest yields observable resonance signal splitting correlating to the enantiomeric excess (e.e.). In this work, symmetry is our lens to explain porphyrin-bas...

Aromaticity is an established and widely used concept for the prediction of the reactivity of organic molecules. However, in on-surface chemistry – where the interaction with the substrate can significantly alter the electronic and geometric structure of the adsorbates – the role of aromaticity is not understood. Here we investigate how aromaticity...

Photodynamic therapy (PDT) is a cancer treatment, which exploits a photosensitizing drug and light to produce reactive oxygen species that can cause selective damage to the target tissue. The second‐generation photosensitizer 5,10,15,20‐tetrakis(m‐hydroxyphenyl)chlorin (m‐THPC) is a widely used, clinically tested, and commercially available drug wi...

Inspired by the rigidified architecture of ‘picket‐fence’ systems, we propose a strategy utilizing strain to impose intramolecular tension in already peripherally overcrowded structures leading to selective atropisomeric conversion. Employing this approach, tuneable shape‐persistent porphyrin conformations were acquired exhibiting distinctive supra...

Porphyrin-based oligomers were synthesized from the condensation of adsorbed 4-benzaldehyde-substituted porphyrins through the formation of C=C linkages, following a McMurry-type coupling scheme. Scanning tunneling microscopy, non-contact atomic force microscopy, and X-ray photoelectron spectroscopy data evidence both the dissociation of aldehyde g...

A Langmuir film of cubane-bridged bisporphyrin (H2por-cubane-H2por) at the air/water interface was developed and characterized. The floating film was successfully employed for the chiral discrimination between l- and d-histidine. The enantioselective behavior persisted after the deposition of the film on a solid support using the Langmuir–Schaefer...

Environmental pollution with chiral organic compounds is an emerging problem requiring innovative sensing methods. Amino-functionalized thioureas, such as 2-(dimethylamino)cyclo-hexyl-(3,5-bis(trifluoromethyl)phenyl)thiourea (Takemoto's catalyst), are widely used organocata-lysts with virtually unknown environmental safety data. Ecotoxicity studies...

Porphyrinoids are pyrrole-containing macrocycles with varied core sizes, which have found many applications beyond the original chemical and biological aspects. Porphyrin research has a long history, covering a wide variety of disciplines of natural sciences, including photosynthesis, P450-related biocatalysis, organic photovoltaic cells, photodyna...

Tetraphenylethylene (TPE) and its derivatives exhibit excellent aggregation‐induced emission (AIE) properties. The TPE unit is easily accessible, and many functional groups can be introduced in a facile manner to yield effective luminescent materials in both solution and the solid‐state. It is because of this, several TPE‐based compounds have been...

The inner core system of metal-free (‘free base’) porphyrins has continually served as a ligand for various metal ions, but it was only recently studied in organocatalysis due its highly tunable basicity. Highly conjugated porphyrin systems offer spectrophotometric sensitivity toward geometrical and/or electronic changes and, thus, utilizing the po...

The development of new antimicrobial strategies that act more efficiently than traditional antibiotics is becoming a necessity to combat multidrug-resistant pathogens. Here we report the efficacy of laser-light-irradiated 5,10,15,20-tetrakis(m-hydroxyphenyl)porphyrin (mTHPP) loaded onto an ethylcellulose (EC)/chitosan (Chs) nanocomposite in eradica...