The effect of translation on the binding energy for transition-metal porphyrines adsorbed on Ag(111) surface

• Luiza Buimaga-Iarinca and
• Cristian Morari

Beilstein J. Nanotechnol. 2019, 10, 706–717, doi:10.3762/bjnano.10.70

• are organo-metallic compounds exhibiting a wide range of optoelectronic, magnetic, and mechanical properties that are interesting for nanotechnology applications ([1][2]. The core of these compounds is porphyrin, a planar heterocycle, formed by four pyrrole moieties [2]. The π-system of porphyrin

• applications can be found in the literature, ranging from molecular sensors [3] over memory devices [4] to light-harvesting structures [5][6][7]. Among all porphyrin compounds, transition-metal porphyrins (TMPPs) are of particularly interest. Because they accommodate a transition-metal atom in the center, the

• . This is a consequence of the fact that self-organization is dominated by the periphery of the porphyrin [32][33][34][35][36][37][38]. As an example, we note the case of mixtures of Co-TPP and Ni-TPP (TPP = tetraphenylporphyrin) on Au(111) forming ordered islands with random distributions of the two

Ultrathin hydrophobic films based on the metal organic framework UiO-66-COOH(Zr)

• Miguel A. Andrés,
• Clemence Sicard,
• Christian Serre,
• Olivier Roubeau and
• Ignacio Gascón

Beilstein J. Nanotechnol. 2019, 10, 654–665, doi:10.3762/bjnano.10.65

• important characteristic in many practical applications. Aguado et al. [37] obtained hydrophobic SIM-2 by post-synthetic functionalization of SIM-1 films deposited onto anodic alumina disks (MOF layer thickness ≈20 µm). Grzybowski et al. [45] obtained freestanding, porphyrin-based MOF films approximately

Electrolyte tuning in dye-sensitized solar cells with N-heterocyclic carbene (NHC) iron(II) sensitizers

• Mariia Karpacheva,
• Catherine E. Housecroft and
• Edwin C. Constable

Beilstein J. Nanotechnol. 2018, 9, 3069–3078, doi:10.3762/bjnano.9.285

• realized with ruthenium-based [2], zinc(II) porphyrin-based [5][6][7][8][9] or metal-free organic dyes [10][11][12]. In a recent review [2], Nazeeruddin points to the fact that only incremental enhancements of the photoconversion efficiencies of ruthenium dyes have occurred during the last two decades

The nanoscaled metal-organic framework ICR-2 as a carrier of porphyrins for photodynamic therapy

• Jan Hynek,
• Sebastian Jurík,
• Martina Koncošová,
• Jaroslav Zelenka,
• Ivana Křížová,
• Tomáš Ruml,
• Kaplan Kirakci,
• Ivo Jakubec,
• František Kovanda,
• Kamil Lang and
• Jan Demel

Beilstein J. Nanotechnol. 2018, 9, 2960–2967, doi:10.3762/bjnano.9.275

• Technology, Technická 5, 166 28 Prague, Czech Republic 10.3762/bjnano.9.275 Abstract Nanosized porphyrin-containing metal-organic frameworks (MOFs) attract considerable attention as solid-state photosensitizers for biological applications. In this study, we have for the first time synthesised and

• these porphyrins allows for superior loading of the nanoparticles when compared with commonly used 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin. The nanoICR-2/porphyrin composites retain part of the free porphyrins photophysical properties, while the photodynamic efficacy is strongly affected by the R

• substituent at the porphyrin phosphinate groups. Thus, phosphinatophenylporphyrin with phenyl substituents has the strongest photodynamic efficacy due to the most efficient cellular uptake. Keywords: metal-organic framework; phosphinic acid based MOF; photodynamic therapy; porphyrin; singlet oxygen

Recent highlights in nanoscale and mesoscale friction

• Andrea Vanossi,
• Dirk Dietzel,
• Andre Schirmeisen,
• Ernst Meyer,
• Rémy Pawlak,
• Thilo Glatzel,
• Marcin Kisiel,
• Shigeki Kawai and
• Nicola Manini

Beilstein J. Nanotechnol. 2018, 9, 1995–2014, doi:10.3762/bjnano.9.190

• porphyrin molecule functionalized by two meso-(3,5-dicyanophenyl) and two meso-(3,5-di-tert-butylphenyl) peripheral rings to the AFM apex, which was then dragged over the surface, as sketched in Figure 6a. Despite the complex molecular structure attached to the tip, atomic-scale patterns and sawtooth

• and the surface plays an important role in the formation of the single-point contact with the copper surface. Of the many internal degrees of freedom of a porphyrin molecule, the σ-bond connecting the porphyrin leg in contact to the surface to the macrocycle was postulated to be the dominant molecular

• the bond-length and bond-angle variations of the porphyrin leg while sliding. Controlling friction and wear by the application of mechanical oscillations and electrostatic forces One way to control friction is to apply an AC voltage between the probing tip and surface [179]. In this experiment, an

Cr(VI) remediation from aqueous environment through modified-TiO₂-mediated photocatalytic reduction

• Rashmi Acharya,
• Brundabana Naik and
• Kulamani Parida

Beilstein J. Nanotechnol. 2018, 9, 1448–1470, doi:10.3762/bjnano.9.137

Heterostuctures of 4-(chloromethyl)phenyltrichlorosilane and 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine prepared on Si(111) using particle lithography: Nanoscale characterization of the main steps of nanopatterning

• Phillip C. Chambers and
• Jayne C. Garno

Beilstein J. Nanotechnol. 2018, 9, 1211–1219, doi:10.3762/bjnano.9.112

• . Nanostructures of CMPS formed within the nanoholes, to furnish spatially selective sites for binding porphyrins. The samples were then characterized with AFM to evaluate the height and morphology of the CMPS nanostructures that had formed within the nanoholes of OTS. The samples were then refluxed in a porphyrin

• matrix of OTS showed minimal areas of nonspecific adsorption. The AFM studies provide insight into the mechanism of the self-polymerization of CMPS as a platform for constructing porphyrin heterostructures. Keywords: atomic force microscopy (AFM); nanostructures; particle lithography; porphyrin; self

• triple-decker sandwich complex of phthalocyanine compounds prepared on graphite was studied using STM by Lei et al. [17]. A method of photocatalytic lithography was reported for making porphyrin surface structures that were applied for preparing protein arrays [18][19]. The assembly of porphyrins at

Adsorption of iron tetraphenylporphyrin on (111) surfaces of coinage metals: a density functional theory study

• Hao Tang,
• Nathalie Tarrat,
• Véronique Langlais and
• Yongfeng Wang

Beilstein J. Nanotechnol. 2017, 8, 2484–2491, doi:10.3762/bjnano.8.248

• ). While the LS ground state is mostly observed in sixfold-coordinated molecular complexes, the ground state of square planar fourfold-coordinated Fe porphyrin can be either IS or HS depending on the functional groups, characterization method or approximation used [2][3][4][5][6][7]. The main difference

• higher by 0.11 eV for S4, and by 0.04 eV for D2d and C2h (Table 1). Note that the IS state was found as ground state in some other calculated results [6][7]. The difficulty for obtaining a proper description of the fundamental state of Fe porphyrin is well known. This is a result of the competition

• ± 0.002 Å in the IS state) by comparison with the free molecule bond length. Furthermore, the side view of the central porphyrin macrocycle of the HS shows a deformation with the Fe atom pointing out of the plane formed by the four N atoms of the pyrrole rings (downwards to the surface) (Figure 5a). This

Towards molecular spintronics

• Georgeta Salvan and
• Dietrich R. T. Zahn

Beilstein J. Nanotechnol. 2017, 8, 2464–2466, doi:10.3762/bjnano.8.245

• theoretical calculations on 2D porphyrin-based networks for spintronics [20]. We are also happy to host a review paper entitled “Spin-chemistry concepts for spintronics scientists” [21], which discusses the vast terminology differences and addresses the benefits that might arise from a stronger interaction

(Metallo)porphyrins for potential materials science applications

• Lars Smykalla,
• Carola Mende,
• Michael Fronk,
• Pablo F. Siles,
• Michael Hietschold,
• Georgeta Salvan,
• Dietrich R. T. Zahn,
• Oliver G. Schmidt,
• Tobias Rüffer and
• Heinrich Lang

Beilstein J. Nanotechnol. 2017, 8, 1786–1800, doi:10.3762/bjnano.8.180

• , which enable a better potential to build molecular spintronic devices [4][5][6][7][8][9]. A crucial step and thus, a prerequisite for the reliable implementation of (metallo)porphyrin-based thin films in a device, is the understanding of the electrical response and local transport properties [10

• alternatives for device approaches such as sensors or organic field-effect transistors (OFETs) [57]. The compatibility of (metallo)porphyrin compounds with deposition techniques of organic molecules presents a great potential for the implementation and scaling down of porphyrins into current device fabrication

• processes, where thin films are required. Therefore, the understanding of the electrical transport properties of (metallo)porphyrin compounds (down to the nanoscale) is a crucial step for a reliable implementation in devices [10]. When performed at the nanoscale level, for example via spectroscopic

Three-in-one approach towards efficient organic dye-sensitized solar cells: aggregation suppression, panchromatic absorption and resonance energy transfer

• Jayita Patwari,
• Samim Sardar,
• Bo Liu,
• Peter Lemmens and
• Samir Kumar Pal

Beilstein J. Nanotechnol. 2017, 8, 1705–1713, doi:10.3762/bjnano.8.171

• , the two organic dyes chosen for co-sensitization are protoporphyrin IX (PPIX) and squarine (SQ2) because of their complementary absorption spectra. From the structure of PPIX (Figure 1a), it is evident that this sensitizer is a derivative of porphyrin, which is an integral part of many naturally

Two-dimensional carbon-based nanocomposites for photocatalytic energy generation and environmental remediation applications

• Suneel Kumar,
• Ashish Kumar,
• Ashish Bahuguna,
• Vipul Sharma and
• Venkata Krishnan

Beilstein J. Nanotechnol. 2017, 8, 1571–1600, doi:10.3762/bjnano.8.159

Synthesis, spectroscopic characterization and thermogravimetric analysis of two series of substituted (metallo)tetraphenylporphyrins

• Rasha K. Al-Shewiki,
• Carola Mende,
• Roy Buschbeck,
• Pablo F. Siles,
• Oliver G. Schmidt,
• Tobias Rüffer and
• Heinrich Lang

Beilstein J. Nanotechnol. 2017, 8, 1191–1204, doi:10.3762/bjnano.8.121

• Institute for Integrative Nanosciences, IFW Dresden, Helmholtzstrasse 20, 01069 Dresden, Germany 10.3762/bjnano.8.121 Abstract Subsequent treatment of H2TPP(CO2H)4 (tetra(p-carboxylic acid phenyl)porphyrin, 1) with an excess of oxalyl chloride and HNR2 afforded H2TPP(C(O)NR2)4 (R = Me, 2; iPr, 3) with

• molecular beam deposition (OMBD), which is attributed to their comparatively low thermal stability as determined by thermogravimetric analysis (TG) of selected representatives. Keywords: electrospray ionization mass spectrometry; IR spectroscopy; metalloporphyrin; porphyrin; thermogravimetry; UV–vis

• porphyrins of the type H2TPP(OH)4 (tetra(p-hydroxyphenyl)porphyrin) [6][7] and MTPP(OMe)4/H2TPP(OMe)4 (tetra(p-methoxyphenyl)porphyrin) (M = Cu [8][9], Ni [9]), cf. Figure 1. The properties of the metalloporphyrins are governed by the (transition) metal ions and the exocyclic moieties on the individual

Selective photodissociation of tailored molecular tags as a tool for quantum optics

• Ugur Sezer,
• Philipp Geyer,
• Moritz Kriegleder,
• Maxime Debiossac,
• Armin Shayeghi,
• Markus Arndt,
• Lukas Felix and
• Marcel Mayor

Beilstein J. Nanotechnol. 2017, 8, 325–333, doi:10.3762/bjnano.8.35

• clusters [10][11][12][13][14][15][16], up to tailored porphyrin derivatives as massive as 10 kDa [17]. In these experiments, every single molecule contained 810 atoms and yet it still needed to be described by a quantum wave function with a de Broglie wavelength of 300–500 fm. The molecular coherence

Ordering of Zn-centered porphyrin and phthalocyanine on TiO₂(011): STM studies

• Piotr Olszowski,
• Lukasz Zajac,
• Szymon Godlewski,
• Bartosz Such,
• Rémy Pawlak,
• Antoine Hinaut,
• Res Jöhr,
• Thilo Glatzel,
• Ernst Meyer and
• Marek Szymonski

Beilstein J. Nanotechnol. 2017, 8, 99–107, doi:10.3762/bjnano.8.11

• the hydroxy groups on the titania surface. However, it was shown that the two equivalent N–H–Obr bonds are formed in the most favored configuration for the porphyrin molecules on TiO2(110) [28]. Formation and ordering of ZnPc/ZnTPP heterostructures In our recent work on CuPc molecule overlayers on

• models of the molecules used in the present study are shown in Figure 8. Basically, we used a Zn atom containing porphyrin and phthalocyanine molecules with a 4-fold symmetry, but for comparison, the Cu-based phthalocyanines are discussed too. Adsorption of ZnPc molecules on the TiO2(011)-(2×1) surface

A dioxaborine cyanine dye as a photoluminescence probe for sensing carbon nanotubes

• Mohammed Al Araimi,
• Petro Lutsyk,
• Anatoly Verbitsky,
• Yuri Piryatinski,
• Mykola Shandura and
• Aleksey Rozhin

Beilstein J. Nanotechnol. 2016, 7, 1991–1999, doi:10.3762/bjnano.7.190

• . Roquelet et al. reported a similar behavior for SWNT–porphyrin complexes, where an overlapping 20 nm split in the porphyrin (Soret) band was observed [21]. Here, the emergence of the 50 nm redshifted peak in the mixtures hinders a strong overlap with the monomer absorption band. The absorption spectrum of

• the quenching of both dyes in the mixtures is approximately the same. Particularly, comparing our systems of SWNTs–surfactant–dye with the system of SWNTs–porphyrin without surfactant, which demonstrated much stronger quenching (ca. 1000 times) [21]. Therefore, in the SWNTs–SDBS–DOB-719 complexes the

Scanning probe microscopy studies on the adsorption of selected molecular dyes on titania

• Jakub S. Prauzner-Bechcicki,
• Lukasz Zajac,
• Piotr Olszowski,
• Res Jöhr,
• Antoine Hinaut,
• Thilo Glatzel,
• Bartosz Such,
• Ernst Meyer and
• Marek Szymonski

Beilstein J. Nanotechnol. 2016, 7, 1642–1653, doi:10.3762/bjnano.7.156

• molecules in the interface layer interact strongly with the substrate, i.e., charge is transferred from the molecule to the substrate. As a consequence, the molecules in the first layer differ much from molecules in the higher overlayers in terms of electronic structure [51]. Porphyrin molecules Porphyrin

• layer [52]. Of the above-mentioned porphyrin species, only 2H-TPP has been studied with STM by Lovat et al. [52]. Similar results were reported by Wang et al. [53]. The molecules adsorb with their plane parallel to the substrate when deposited at room temperature, as expected from the results of the

• orientation change, and consequently, the STM image of the porphyrin molecule changes as well (Figure 4) [53]. The saddle-shape conformation characteristic of 2H-TPP changes into a flat conformation. Additionally, the NiTPP molecules rotate by 45° with respect to the 2H-TPP species. And finally, the STM image

Filled and empty states of Zn-TPP films deposited on Fe(001)-p(1×1)O

• Gianlorenzo Bussetti,
• Alberto Calloni,
• Rossella Yivlialin,
• Andrea Picone,
• Federico Bottegoni and
• Marco Finazzi

Beilstein J. Nanotechnol. 2016, 7, 1527–1531, doi:10.3762/bjnano.7.146

• and the interface dipole was determined and compared with data available in the literature. Keywords: inverse photoemission; metal-oxide film; OMBE; porphyrin; Introduction Thin organic films can be realized by depositing single molecules on surfaces, which is the first step for the so-called bottom

• porphyrin reactivity [1]. In particular, the metal atom is placed in the middle of the main cavity of the porphyrin, which has a planar structure, allowing the metal atom to interact from both sides of the molecule. The molecule–substrate interaction can be interpreted in terms of a bond between a special

• ligand (the surface) and the porphyrin (the so-called surface trans effect (STE)) [1][7]. In order to avoid this problem, porphyrin films are usually grown on passivated surfaces [1] or, conversely, thick (on the order of a few nanometers) films are exploited [8]. A possible alternative is the use of

Hierarchical coassembly of DNA–triptycene hybrid molecular building blocks and zinc protoporphyrin IX

• Rina Kumari,
• Sumit Singh,
• Mohan Monisha,
• Sourav Bhowmick,
• Anindya Roy,
• Neeladri Das and
• Prolay Das

Beilstein J. Nanotechnol. 2016, 7, 697–707, doi:10.3762/bjnano.7.62

• are biologically highly relevant molecules and their biocompatibility is notable. Porphyrin derivatives are widely used as photosensitizers in PDT to produce reactive oxygen species (ROS). Reportedly, Zn PpIX can interact with dsDNA in “outside stacking mode”. Therefore, the rationale to use Zn PpIX

Rigid multipodal platforms for metal surfaces

• Michal Valášek,
• Marcin Lindner and
• Marcel Mayor

Beilstein J. Nanotechnol. 2016, 7, 374–405, doi:10.3762/bjnano.7.34

• , temperature, or deposition time as determined by IR analysis. Recently, Dong and co-workers have synthetized a self-decoupled porphyrin with a tetraphenylmethane tripodal anchor 38 (Figure 16) and deposited it on Au(111) using different wet-chemistry methods in order to assemble a single molecule

• electroluminescence STM experiment (Figure 17) [74]. The rigid tripodal anchor in this molecule not only acts as a robust decoupling spacer but also controls the orientation of the porphyrin molecule in the desired up-right standing position along the tip axial direction. STM images revealed the formation of

• STM tip resonantly tunnels into an excited state of the porphyrin molecule 38 strongly bounded to the gold surface, and the excited molecule then decays radiatively back to the ground

Early breast cancer screening using iron/iron oxide-based nanoplatforms with sub-femtomolar limits of detection

• Dinusha N. Udukala,
• Hongwang Wang,
• Sebastian O. Wendel,
• Aruni P. Malalasekera,
• Thilani N. Samarakoon,
• Asanka S. Yapa,
• Gayani Abayaweera,
• Matthew T. Basel,
• Pamela Maynez,
• Raquel Ortega,
• Yubisela Toledo,
• Leonie Bossmann,
• Colette Robinson,
• Katharine E. Janik,
• Olga B. Koper,
• Ping Li,
• Massoud Motamedi,
• Daniel A. Higgins,
• Gary Gadbury,
• Gaohong Zhu,
• Deryl L. Troyer and
• Stefan H. Bossmann

Beilstein J. Nanotechnol. 2016, 7, 364–373, doi:10.3762/bjnano.7.33

• is a vital strategy for early cancer detection. Water-dispersable Fe/Fe3O4-core/shell based nanoplatforms for protease detection are capable of detecting protease activity down to sub-femtomolar limits of detection. They feature one dye (tetrakis(carboxyphenyl)porphyrin (TCPP)) that is tethered to

• of detecting protease activities over a wide activity range down to sub-femtomolar LOD’s. These nanoplatforms consist of dopamine-covered, water-dispersable iron/iron oxide core/shell nanoparticles, to which one fluorescent dye (TCPP, tetrakis(carboxyphenyl)porphyrin) is tethered via a consensus

• protease detection. For each protease, a highly selective oligopeptide is used to tether tetrakis-carboxy-phenyl-porphyrin (TCPP) to the nanoparticle. Cyanine 5.5 is linked permanently to the Fe/Fe3O4 nanoparticles. Figure 1 is reproduced from [23] with permission. Mechanistic scheme of the “light switch

Conformational switching of ethano-bridged Cu,H₂-bis-porphyrin induced by aromatic amines

• Simona Bettini,
• Emanuela Maglie,
• Rosanna Pagano,
• Victor Borovkov,
• Yoshihisa Inoue,
• Ludovico Valli and
• Gabriele Giancane

Beilstein J. Nanotechnol. 2015, 6, 2154–2160, doi:10.3762/bjnano.6.221

• Heritage, University of Salento, Via per Arnesano, Lecce, Italy 10.3762/bjnano.6.221 Abstract Cu,H2-bis-porphyrin (Cu,H2-Por2), in which copper porphyrin and free-base porphyrin are linked together by an ethano-bridge, was dissolved in chloroform and spread at the air/liquid subphase interface of a

• Langmuir trough. The bis-porphyrin derivative, floating film was characterized by reflection spectroscopy and the surface pressure of the floating film was studied as a function of the mean area per molecule. When aromatic amines are dissolved in the subphase, an evident interaction between the bis

• -porphyrin host and the aromatic amine guest is observed. A clear-cut variation of the profile of surface pressure vs area per molecule curve is observed. Reflection spectroscopy highlights that the aromatic amines dissolved in the subphase are able to induce the syn-to-anti conformational switching in the

Electrospray deposition of organic molecules on bulk insulator surfaces

• Antoine Hinaut,
• Rémy Pawlak,
• Ernst Meyer and
• Thilo Glatzel

Beilstein J. Nanotechnol. 2015, 6, 1927–1934, doi:10.3762/bjnano.6.195

• , ESI has been successfully applied to deposit triply fused porphyrin molecules on an insulating KBr(001) surface in UHV environment. Different deposition coverages have been obtained and characterization of the surface by in-situ atomic force microscopy working in the non-contact mode shows details of

• molecules which are more suitable for future devices and could incorporate additional functions and anchoring groups. In this work we present the adaptation of a UHV-ESI system to deposit triply fused porphyrin molecules on a bulk insulator KBr(001) sample and the analysis of theses deposits by high

• surface but are diffusing to fast for nc-AFM imaging. Large coverage UHV-ESI of triply fused diporphyrins The complex porphyrin-based molecules under study are schematically shown in Figure 3a. It is a triply fused diporphyrin molecule including two 3-cyanophenyl groups and Zn metal cores. Similar

Electron and heat transport in porphyrin-based single-molecule transistors with electro-burnt graphene electrodes

• Hatef Sadeghi,
• Sara Sangtarash and
• Colin J. Lambert

Beilstein J. Nanotechnol. 2015, 6, 1413–1420, doi:10.3762/bjnano.6.146

• Hatef Sadeghi Sara Sangtarash Colin J. Lambert Quantum Technology Centre, Physics Department, Lancaster University, Lancaster, LA1 4YB, UK 10.3762/bjnano.6.146 Abstract We have studied the charge and thermal transport properties of a porphyrin-based single-molecule transistor with electro-burnt

• graphene electrodes (EBG) using the nonequilibrium Green’s function method and density functional theory. The porphyrin-based molecule is bound to the EBG electrodes by planar aromatic anchor groups. Due to the efficient π–π overlap between the anchor groups and graphene and the location of frontier

• configurations at the electrodes. This can lead to rectification in the current–voltage characteristic of the junction. Keywords: electro-burnt graphene electrodes; nanoelectronics; porphyrin; single-molecule transistor; Introduction Transistors are the fundamental building blocks of modern electronic devices

Nanobioarchitectures based on chlorophyll photopigment, artificial lipid bilayers and carbon nanotubes

• Marcela Elisabeta Barbinta-Patrascu,
• Stefan Marian Iordache,
• Ana Maria Iordache,
• Nicoleta Badea and
• Camelia Ungureanu

Beilstein J. Nanotechnol. 2014, 5, 2316–2325, doi:10.3762/bjnano.5.240

• the artificial lipid bilayers (DPPC:Chol molar ratio = 4:1), which were suspended in a safe bio-dispersant of phosphate buffer solution (PB, KH2PO4–Na2HPO4, pH 7.4). Chlorophyll a (Chla), a natural antioxidant porphyrin, was extracted from spinach leaves according to the Strain and Svec method [23

• successfully used as a spectral marker to obtain information at the molecular level in the artificial lipid bilayers. This enabled spectral monitoring of the bio-based composites by exploiting the fluorescence emission properties and strong visible absorption of the porphyrin macrocycle. The procedure for