Porphyrins and related macrocycles have been studied broadly for their applications in medicine and materials because of their tunable physicochemical, optoelectronic and magnetic properties. In this review article, we focused on the applications of fluorinated porphyrinoids and their supramolecular systems and summarized the reports published on these chromophores in the past 5-6 years. The commercially available fluorinated porphyrinoids: meso-perfluorophenylporphyrin (TPPF20 ) perfluorophthalocyanine (PcF16 ) and meso-perfluorophenylcorrole (CorF15 ) have increased photo and oxidative stability due to the presence of fluoro groups. Because of their tunable properties and robustness toward oxidative damage these porphyrinoid-based chromophores continue to gain attention of researchers developing advanced functional materials for applications such as sensors, photonic devices, component for solar cells, biomedical imaging, theranostics and catalysts.

Reactions of Mn(O2CMe)(2)center dot nH(2)O (n = 0 and 4) with the ligand o-R2AsC6H4CO2H (where, R = alkyl substituent such as -CH3 (Me), -C2H5 (Et), and -C6H11) formed nine oxomanganese (II)-arsine oxide complexes: [Mn2O{(o-R2As(O)C6HCO2)(2)(H2O)n}]center dot n'H2O] {R = -Me, n = 3; n' = 0 (three isomers); R = -Et, n = 3, n' = 0; n = 5, n' = 1, 2; R =C6H11, n = 5, n' = 0 (two isomers), n = 1, n' = 0) in the presence of both moisture and oxygen. The prepared complexes were characterized by IR, UV-Vis, and EPR spectroscopic techniques and were further confirmed by measuring their magnetic susceptibility, thermal and molar conductance.The formation of two different types of complexes was due to the difference in the inductive effect of aryl and the alkyl substituent and the change of the counter-anion, i.e., chloride and acetate and their role significantly helped in deciding the formation of oxomanganese(II)-arsine oxide or oxomanganese(II)-arsine complexes.

We report here an alternate redesigned five-step synthesis of 2,6-diacetamido-4-formylpyridine. The method described here is more convenient where this aldehyde is prepared in commercially viable quantities from simple and easy-to-use reagents and is a key compound required to prepare 5,10,15,20-Tetrakis(3,5-diacetamido-4-pyridyl)porphyrin (I). This porphyrin can be used as an excellent building block for the construction of supramolecular assemblies and is an interesting compound to study the design, principles, and photonic properties such as the extent of electron and energy transfer.

Herein we describe the design, efficient synthesis, and photophysical properties of two macrocycle dyes for cancer theranostics. This study compares a glycosylated chlorin with a glycosylated phthalocyanine designed to specifically target cancer, wherein the photophysical properties enable both fluorescence imaging and the sensitization of the formation of reactive oxygen species (ROS) for photodynamic therapy. Both the compounds show low darktoxicity (IC50 > 100 mu M). The glycosylated phthalocyanine showed low phototoxicity (IC50 > 100 mu M) while glycosylated chlorin showed high phototoxicity (IC50 = 1-2 mu M). ZnPcGlc(8) has low solubility and also form aggregates in aqueous media, thus resulting in minimal uptake in two different human breast cancer cell lines: MDA-MB-231 and MCF-7. The glycosylated chlorin however was efficiently taken up by these two cell lines, thus allows fluorescence imaging in cells and in xenograft tumor model in mice. In this study, we find that the chlorin conjugate is the more promising theranostic agent.

Porphyrin-based molecules are actively studied as dual function theranostics: fluorescence-based imaging for diagnostics and fluorescence-guided therapeutic treatment of cancers. The intrinsic fluorescent and photodynamic properties of the bimodal molecules allows for these theranostic approaches. Several porphyrinoids bearing both hydrophilic and/or hydrophobic units at their periphery have been developed for the aforementioned applications, but better tumor selectivity and high efficacy to destroy tumor cells is always a key setback for their use. Another issue related to their effective clinical use is that, most of these chromophores form aggregates under physiological conditions. Nanomaterials that are known to possess incredible properties that cannot be achieved from their bulk systems can serve as carriers for these chromophores. Porphyrinoids, when conjugated with nanomaterials, can be enabled to perform as multifunctional nanomedicine devices. The integrated properties of these porphyrinoid-nanomaterial conjugated systems make them useful for selective drug delivery, theranostic capabilities, and multimodal bioimaging. This review highlights the use of porphyrins, chlorins, bacteriochlorins, phthalocyanines and naphthalocyanines as well as their multifunctional nanodevices in various biomedical theranostic platforms.

Self-assembled monolayers of thiol terminated conjugated diacetylenes can be cross-linked using ultraviolet light to form highly conjugated polydiacetylenic conductive monolayers [1]; however, the reported syntheses of the diacetylene monomers present numerous problems that prevent the wide spread application of these in functional materials. We report a redesigned four-step synthesis that proceeds in 75-80% overall yields and allows gram scale production of an array of thiol terminated conjugated diacetylenes, thereby allowing examination and application of these low-dimensional conductive materials. (C) 2018 Elsevier Ltd. All rights reserved.

Photodynamic therapy (PDT) is a non-invasive treatment widely applied to different cancers. The goal of PDT is the photo-induced destruction of cancer cells by the activation of different cell death mechanisms, including apoptosis and/or necrosis. Recent efforts focusing on understanding the mechanisms of cell death activated by PDT find that it depends on the type of photosensitizer (PS), targeted organelles, and nature of the light used. It is generally accepted that very short incubation times are required to direct the PS to the plasma membrane (PM), while longer periods result in the accumulation of the PS in internal compartments such as the endoplasmic reticulum or mitochondria. Glycosylation of the PS targets cancer via saccharide receptors on the cell surface, and is generally assumed that these compounds rapidly internalize and accumulate, e.g. in the endoplasmic reticulum. Herein we demonstrate that a minor fraction of a glycosylated chlorin compound residing at the PM of cancer cells can activate necrosis upon illumination by compromising the PM independently of the length of the incubation period. The results presented here show that the PM can also be targeted by glycosylated PS designed to accumulate in internal organelles. PS activation to induce necrosis by compromising the plasma membrane has the benefits of fast cell death and shorter irradiation times. The findings described here expand our understanding of the cellular damage induced by phototherapies, presenting the possibility of activating another cell death mechanism based on the incubation time and type of light used.

NMR, IR and Raman spectroscopic studies were used to probe the presence of MLCT phenomenon in four macrocyclic diamagnetic hexa-coordinate complexes: [L3Fe] 2+ and [L3Co] 3+ , where (L= 2,2  -bipyridine and 1,10-phenanthroline) by DFT implemented in ADF.2012.01 After pre-optimization of complexes, the NMR parameters: Chemical Shifts of constituents (δ M n+ , δ 14 N, δ 13 C, and δ 1 H), their total NMR shielding tensors (σM n+ , σ 14 N, σ 13 C, and σ 1 H) containing 2 diamagnetic and 4 paramagnetic contributions, k and j were obtained by using the “NMR Program” with Single Point, LDA or GGA, Default, None, Collinear, Nosym using TZP or TZ2P Basis sets leaving Unrestricted command blank. IR and Raman frequencies of normal modes of Fundamental vibration bands of complexes were obtained by using Frequencies and Raman full key points. Values of two NMR parameters (σ, δ) inferred that the 24 Hydrogens were of 4 different types and all the 6 Nitrogens were of the same type in all of the four studied complexes. However in tris(Bipy) complexes, the 30 Carbons belonged to 5 different types while the 36 Carbons showed 6 different types in tris(Phen) complexes. NMR parameter (H Spin ) for all of the four complexes was calculated. The presence of MLCT phenomenon in these complexes was confirmed by a large increase in σ 14 N values for coordinated ligands in these complexes relative to the uncoordinated ligands. The 177 and 195 vibration bands of the two types of complexes respectively were classified into vibration symmetries, IR and Raman activities. Some thermal parameters such as zero point energy, entropy, internal energy and constant volume capacity of the complexes were also calculated and reported here.

DFT implemented in ADF.2012.01 was applied to study the structures of three macrocyclic paramagnetic hexa coordinate complexes: [L 3 M] 2+ {M=V(II), Ni(II)}, and [L 3 Cr] 3+ (L=2,2  -bipyridine) by four spectral techniques.After their pre-optimization, the software was run by using Single Point, LDA, Default, Relativity, Spin Orbit, ZORA, Unrestricted, None, Collinear, Nosym using TZP or TZ2P Basis sets in ESR/EPR/EFG/ZFS Program to obtain ESR parameters: g 11 , g 22 , g 33 , g iso , a 11 , a 22 , a 33 , A ten .More ESR parameters (g n .A ten , ZFS) and NQR parameters {, q 11 , q 22 , q 33 , NQCC} were obtained by replacing Spin Orbit by scalar command in a new ADF Input.The software was, then, run using the "NMR Program" with Single Point, Default, None, Collinear, Nosym using the same Basis sets leaving unrestricted command blank to obtain Shielding Constants (σM, σ 13 C, σ 17 O), Chemical Shifts (δM, δ 13 C, δ 17 O), two diamagnetic, four paramagnetic and four spin orbit contributing terms in σ values of the constituents.The software was also run to obtain IR frequencies of normal modes of the (3n-6) fundamental vibration bands of the complexes.Five parameters: σ, δ, g.A ten , , NQCC of 14 N; four parameters: σ, δ, g.A ten ,  of 13 C and three parameters: σ, δ, g.A ten, of 1 H corroborated to infer that the 30 Carbons were of 5 different types, the 24 Hydrogens were of 4 different types but the 6 Nitrogens were of the same type spatially in the three studied complexes.This study was important because we could confirm MLCT phenomenon by NMR; calculated four more NMR, ESR and NQR parameters: H^, E hf, Asymmetric coefficient (), Laplace equation; classified the 177 bands into their vibration symmetries and IR activities and calculated some thermal parameters of the complexes.

Nitro-porphyrins are an important class of commercial dyes with a range of potential applications. The nitro group is known to dramatically affect the photophysics of the porphyrin, but there are few systematic investigations of the contributing factors. To address this deficiency, we present spectroscopic studies of a series of nitro-porphyrins, accompanied by density functional theory calculations to elucidate their structures. In particular, we explore how the positions of the substituents affect the energy levels and nuclear geometry. As expected, nitro groups on the meso-phenyl rings cause small changes to the orbital energies by induction, while those at the β-pyrrole positions more strongly conjugate into the aromatic system. In addition, however, we find evidence that β-pyrrole nitro groups distort the porphyrin, creating two non-planar conformations with distinct properties. This unexpected result helps explain the anomalous photophysics of nitro-porphyrins reported throughout the literature, including inhomogeneous line broadening and biexponential fluorescence decay. © 2017 Wiley Periodicals, Inc.

DFT implemented in ADF 2012.01 was applied to 9 bi-nuclear transition metal carbonyls: [M2(CO)10], (M=Mn, Tc, Re), [Co(CO)4MCo(CO)4], (M=Zn, Cd, Hg), [Fe2(CO)9], [terminal Co2(CO)8] and [bridged Co2(CO)8] to obtain the Shielding Constants (σ M, σ 13 C, σ 17 O), Chemical Shifts (δ M, δ 13 C, δ 17 O), two diamagnetic and four paramagnetic contributing terms in the σ values of constituents. The software was also run with Frequencies and Raman full to obtain frequencies of the normal modes of all the (3n-6) Fundamental vibration bands of the carbonyls. Neither of two metals nor any two carbonyls (Cos) were found to be both spatially and magnetically equivalent. In eight of the nine carbonyls, the two metals were only spatially equivalent along with many CO groups. A perturbing metal and spatially equivalent responding metal along with spatially equivalent CO groups had same k and j values respectively. The importance of this study would lie in the fact that using these parameters, we successfully studied 4 characteristics: spatial displacements/ stereochemical equivalences of constituents; calculated Effective Spin Hamiltonian (H Spin ) of metals and 13 C nuclei, obtained Coordination Shifts (Δδ 13 C, Δδ 17 O); lent credence to IR / Raman results in supporting the πacidity of carbonyls which were never studied by Comutational NMR methods.

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTGlycosylated Porphyrins, Phthalocyanines, and Other Porphyrinoids for Diagnostics and TherapeuticsSunaina Singh*†, Amit Aggarwal*†, N. V. S. Dinesh K. Bhupathiraju*‡, Gianluca Arianna‡, Kirran Tiwari‡, and Charles Michael Drain‡§View Author Information† Department of Natural Sciences, LaGuardia Community College of the City University of New York, Long Island City, New York 11101, United States‡ Department of Chemistry and Biochemistry, Hunter College of the City University of New York, New York, New York 10065, United States§ The Rockefeller University, New York, New York 10065, United States*E-mail: [email protected]*E-mail: [email protected]*E-mail: [email protected]Cite this: Chem. Rev. 2015, 115, 18, 10261–10306Publication Date (Web):August 28, 2015Publication History Received28 April 2015Published online28 August 2015Published inissue 23 September 2015https://doi.org/10.1021/acs.chemrev.5b00244Copyright © 2015 American Chemical SocietyRIGHTS & PERMISSIONSArticle Views9355Altmetric-Citations392LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit Read OnlinePDF (15 MB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information SUBJECTS:Carbohydrates,Cells,Conjugate acid-base pairs,Dyes and pigments,Pyrroles Get e-Alerts

AbstractElectron‐poor 15N‐safranine analogues are prepared via Ullmann coupling.

Safranines hold great promise as artificial flavin-like electron transfer cofactors with tunable properties. We have previously reported the stepwise synthesis of a safranine analogue, p-methoxy safranine. We now report an improved synthetic pathway which enables the synthesis of safranine analogues containing electron donating phenyl substituents. Low potential safranine analogues were synthesized that extend the range of two electron midpoint reduction potentials to 249mV, or 11.4kcal/mol. NMR analysis of the safranine series demonstrates that the 15N chemical shift at the N(5) position correlates with the two-electron reduction midpoint potential.

A triply bridged fused diporphyrin appended with six thioglucose units is reported. This new, chemically and photochemically stable amphiphilic compound is taken up by breast cancer cells and causes cell death upon light exposure. Photophysical studies reveal absorption bands in the near IR region, and photosensitized formation of singlet oxygen in high quantum yields.