Construction of a Lung Adenocarcinoma Prognostic Model Utilizing Serine and Glycine Metabolism-Related Genes.

The objective of this study was to construct a prognostic model by utilizing serine/glycine metabolism-related genes (SGMGs), thus establishing a risk score for lung adenocarcinoma (LUAD). Based on the TCGA-LUAD and SGMG data set, two subtypes with different SGMG expression levels were identified by clustering analysis. Thirteen differential expression genes were used to construct RiskScore by Cox regression. GSE72094 data set was used for validation. The survival characteristics, immune features, and potential benefits of chemotherapy drugs were analyzed for two risk groups. RiskScore was constructed based on the genes ABCC12, RIC3, CYP4B1, SFTPB, CACNA2D2, IGF2BP1, NTSR1, DKK1, CREG2, PITX3, RGS20, FETUB, and IGFBP1. Patients in the low-risk (LR) group exhibited a superior overall survival. In addition, aDCs, iDSs, mast cells, neutrophils, HLA, and type II IFN were more abundant in the LR group with higher IPS scores and lower TIDE scores. In contrast, NK cells, APC coinhibition, and MHC-I were more common in the high-risk (HR) group, which may be more sensitive to chemotherapy drugs such as cisplatin, oxaliplatin, and nilotinib. RiskScore was a promising biomarker that can be used to distinguish LUAD prognosis, immune features, and sensitivity to chemotherapy drugs.

Constructing 2D Phthalocyanine Covalent Organic Framework with Enhanced Stability and Conductivity via Interlayer Hydrogen Bonding as Electrocatalyst for CO2 Reduction.

Fabricating COFs-based electrocatalysts with high stability and conductivity still remains a great challenge. Herein, 2D polyimide-linked phthalocyanine COF (denoted as NiPc-OH-COF) is constructed via solvothermal reaction between tetraanhydrides of 2,3,9,10,16,17,23,24-octacarboxyphthalocyaninato nickel(II) and 2,5-diamino-1,4-benzenediol (DB) with other two analogous 2D COFs (denoted as NiPc-OMe-COF and NiPc-H-COF) synthesized for reference. In comparison with NiPc-OMe-COF and NiPc-H-COF, NiPc-OH-COF exhibits enhanced stability, particularly in strong NaOH solvent and high conductivity of 1.5 × 10-3  S m-1 due to the incorporation of additional strong interlayer hydrogen bonding interaction between the O-H of DB and the hydroxy "O" atom of DB in adjacent layers. This in turn endows the NiPc-OH-COF electrode with ultrahigh CO2 -to-CO faradaic efficiency (almost 100%) in a wide potential range from -0.7 to -1.1 V versus reversible hydrogen electrode (RHE), a large partial CO current density of -39.2 mA cm-2 at -1.1 V versus RHE, and high turnover number as well as turnover frequency, amounting to 45 000 and 0.76 S-1 at -0.80 V versus RHE during 12 h lasting measurement.

Unprecedented POSS-Linked 3D Covalent Organic Frameworks with 2-Fold Interpenetrated scu or sqc Topology Regulated by Porphyrin Center for Photocatalytic CO2 Reduction.

The synthesis and characterization of porphyrin center regulated three-dimensional covalent organic frameworks (COFs) with 2-fold interpenetrated scu or sqc topology have been investigated. These COFs exhibit unique structural features and properties, making them promising candidates for photocatalytic applications in CO2 reduction and artemisinin synthesis. The porphyrin center serves as an anchor for metal ions, allowing precise control over structures and functions of the frameworks. Furthermore, the metal coordination within the framework imparts desirable catalytic properties, enabling their potential use in photocatalytic reactions. Overall, these porphyrin center regulated metal-controlled COFs offer exciting opportunities for the development of advanced materials with tailored functionalities.

12 Connecting Sites Linked Three-dimensional Covalent Organic Frameworks with Intrinsic Non-interpenetrated shp Topology for Photocatalytic H2O2 Synthesis.

Developing high connectivity (>8) three-dimensional (3D) covalent organic frameworks (COFs) towards new topologies and functions remains a great challenge owing to the difficulty in getting high connectivity organic building blocks. This however represents the most important step towards promoting the diversity of COFs due to the still limited dynamic covalent bonds available for constructing COFs at this stage. Herein, highly connected phthalocyanine-based (Pc-based) 3D COFs MPc-THHI-COFs (M=H2, Ni) were afforded from the reaction between 2,3,9,10,16,17,23,24-octacarboxyphthalocyanine M(TAPc) (M=H2, Ni) and 5,5',5'',5''',5'''',5'''''-(triphenylene-2,3,6,7,10,11-hexayl)hexa(isophthalohydrazide) (THHI) with 12 connecting sites. Powder X-ray diffraction analysis together with theoretical simulations and transmission electron microscopy reveals their crystalline nature with an unprecedented non-interpenetrated shp topology. Experimental and theoretical investigations disclose the broadened visible light absorption range and narrow optical band gap of MPc-THHI-COFs. This in combination with their 3D nanochannels endows them with efficient photocatalysis performance for H2O2 generation from O2 and H2O via 2e- oxygen reduction reaction and 2e- water oxidation reaction under visible-light irradiation (λ >400 nm). This work provides valuable result for the development of high connectivity functional COFs towards diverse application potentials.

Highly Connected Three-Dimensional Covalent Organic Framework with Flu Topology for High-Performance Li-S Batteries.

Lithium-sulfur batteries (LSBs) have been considered as a promising candidate for next-generation energy storage devices, which however still suffer from the shuttle effect of the intermediate lithium polysulfides (LiPSs). Covalent-organic frameworks (COFs) have exhibited great potential as sulfur hosts for LSBs to solve such a problem. Herein, a pentiptycene-based D2h symmetrical octatopic polyaldehyde, 6,13-dimethoxy-2,3,9,10,18,19,24,25-octa(4'-formylphenyl)pentiptycene (DMOPTP), was prepared and utilized as a building block toward preparing COFs. Condensation of DMOPTP with 4-connected tetrakis(4-aminophenyl)methane affords an expanded [8 + 4] connected network 3D-flu-COF, with a flu topology. The non-interpenetrated nature of the flu topology endows 3D-flu-COF with a high Brunauer-Emmett-Teller surface area of 2860 m2 g-1, large octahedral cavities, and cross-linked tunnels in the framework, enabling a high loading capacity of sulfur (∼70 wt %), strong LiPS adsorption capability, and facile ion diffusion. Remarkably, when used as a sulfur host for LSBs, 3D-flu-COF delivers a high capacity of 1249 mA h g-1 at 0.2 C (1.0 C = 1675 mA g-1), outstanding rate capability (764 mA h g-1 at 5.0 C), and excellent stability, representing one of the best results among the thus far reported COF-based sulfur host materials for LSBs and being competitive with the state-of-the-art inorganic host materials.

Reticular Synthesis of Metal-Organic Frameworks by 8-Connected Quadrangular Prism Ligands for Water Harvesting.

Utilization of rigid, highly connected organic linkers is critical for the reticular synthesis of functional metal-organic frameworks (MOFs). However, highly-stable MOFs (e.g. Al/Cr/Zr-based MOFs) based on rigid ligands with more than 6 coordinating functions have been rarely achieved thus far. Herein, we describe the construction of two bcu Zr-based MOFs (named ZrMOF-1 and ZrMOF-2) from peripherally extended pentiptycene ligands (H8 PEP-1 and H8 PEP-2) with rigid quadrangular prism shape possessing 8 carboxylic groups at the prism vertices. Particularly, ZrMOF-1 exhibits microporous structure with large Bruno-Emmett-Teller surface area and high water stability, endowing it a promising water harvesting material with a high water uptake capacity of 0.83 gH2O gMOF -1 at P/P0 =0.90 and 25 °C, a steep uptake at a low P/P0 of 0.30, and excellent durability over 500 water adsorption-desorption cycles. Moreover, self-consistent charge density functional tight-binding calculations were carried out, rationalizing the water adsorbing process and amount in ZrMOF-1.

Post-Nickelation of a Crystalline Trinuclear Copper Organic Framework for Synergistic Photocatalytic Carbon Dioxide Conversion.

Rational regulation of electronic structures and functionalities of framework materials still remains challenging. Herein, reaction of 4,4',4''-nitrilo-tribenzhydrazide with tris(µ2 -4-carboxaldehyde-pyrazolato-N,N')-tricopper (Cu3 Py3 ) generates the crystalline copper organic framework USTB-11(Cu). Post-modification with divalent nickel ions affords the heterometallic framework USTB-11(Cu,Ni). Powder X-ray diffraction and theoretical simulations reveal their two-dimensional hexagonal structure geometry. A series of advanced spectroscopic techniques disclose the mixed CuI /CuII state nature of Cu3 Py3 in USTB-11(Cu,Ni) with a uniform bistable Cu3 4+ (CuI 2 CuII ) : Cu3 5+ (CuI CuII 2 ) (ca. 1 : 3) oxidation state, resulting in a significantly improved formation efficiency of the charge-separation state. This endows the Ni sites with enhanced activity and USTB-11(Cu,Ni) with outstanding photocatalytic CO2 to CO performance with a conversion rate of 22 130 µmol g-1 h-1 and selectivity of 98 %.

Piperazine-Linked Metalphthalocyanine Frameworks for Highly Efficient Visible-Light-Driven H2O2 Photosynthesis.

Artificial photosynthesis of H2O2 from O2 reduction provides an energy-saving, safe, and green approach. However, it is still critical to develop highly active and selective 2e- oxygen reduction reaction photocatalysts for efficient H2O2 production owing to the unsatisfactory photosynthesis productivity. Herein, two new two-dimensional piperazine-linked CoPc-based covalent organic frameworks (COFs), namely, CoPc-BTM-COF and CoPc-DAB-COF, were afforded from the nucleophilic substitution reaction of hexadecafluorophthalocyaninato cobalt(II) (CoPcF16) with 1,2,4,5-benzenetetramine (BTM) or 3,3'-diaminobenzidine (DAB). Powder X-ray diffraction analysis in combination with electron microscopy and a series of spectroscopic technologies reveals their crystalline porous framework with a fully conjugated structure and eclipsed π-stacking model. Ultraviolet-visible diffuse reflectance absorption spectra unveil their excellent light absorption capacity in a wide range of 400-1000 nm. This, together with their enhanced photo-induced charge separation and transport efficiency as disclosed by photocurrent response and photoluminescence measurements, endows the as-prepared piperazine-linked CoPc-based COFs with superior photocatalytic activity toward O2-to-H2O2 conversion under visible-light irradiation (λ > 400 nm). In particular, CoPc-BTM-COF exhibits a record-high H2O2 yield of 2096 µmol h-1 g-1 among the COF-based photocatalysts and an impressive apparent quantum yield of 7.2% at 630 nm. The present result should be helpful for fabricating high-performance and low-cost photocatalysts for visible-light-driven H2O2 photosynthesis.

Conjugated Three-Dimensional High-Connected Covalent Organic Frameworks for Lithium-Sulfur Batteries.

Developing conjugated three-dimensional (3D) covalent organic frameworks (COFs) still remains an extremely difficult task due to the lack of enough conjugated 3D building blocks. Herein, condensation between an 8-connected pentiptycene-based D2h building block (DMOPTP) and 4-connected square-planar linkers affords two 3D COFs (named 3D-scu-COF-1 and 3D-scu-COF-2). A combination of the 3D homoaromatic conjugated structure of the former building block with the 2D conjugated structure of the latter linking units enables the π-electron delocalization over the whole frameworks of both COFs, endowing them with excellent conductivities of 3.2-3.5 × 10-5 S cm-1. In particular, the 3D rigid quadrangular prism shape of DMOPTP guides the formation of a twofold interpenetrated scu 3D topology and high-connected permanent porosity with a large Brunauer-Emmett-Teller (BET) surface area of 2340 and 1602 m2 g-1 for 3D-scu-COF-1 and 3D-scu-COF-2, respectively, ensuring effective small molecule storage and mass transport characteristics. This, in combination with their good charge transport properties, renders them promising sulfur host materials for lithium-sulfur batteries (LSBs) with high capacities (1035-1155 mA h g-1 at 0.2 C, 1 C = 1675 mA g-1), excellent rate capabilities (713-757 mA h g-1 at 5.0 C), and superior cycling stability (71-83% capacity retention at 2.0 C after 500 cycles), surpassing the most of organic LSB cathodes reported thus far.

General Design Strategy of Anti-aromatic Porphyrinoids.

A systematic investigation to arrange the typical anti-aromatic porphyrinoids in sequence was performed. Based on density functional theory calculations, six rules are summarized to obtain the high-performance anti-aromatic porphyrinoids: (1) when two atoms are deleted/added on the 18π electron current ring flowing pipe, we will immediately obtain a 16π/20π electron anti-aromatic system; (2) it is a good idea to increase the number of pyrrole/thiophen/furan units on the π-electron current ring flowing pipe; (3) the heteroatom selecting order is -O- (optimal choice), -NH- (second choice), and -S- (last choice); (4) it is worth noting that the C-C=C-C unit is not beneficial for the anti-aromatic properties; (5) it is very significant to avoid the crowded environment in the core space of an anti-aromatic molecule. In this view, -O- is much better than -S- and -NH-; (6) the "circular" skeleton is much better than an "ellipse-like", "rectangular", or "parallelogram-like" one.

Enhanced Photocatalytic CO2 Reduction through Hydrophobic Microenvironment and Binuclear Cobalt Synergistic Effect in Metallogels.

Assemblies that mimic natural lipid bilayers are theoretically efficient for photocatalytic CO2 reduction; however, such an approach has not been yet explored. Herein, metallogels (LG/Nico-Co) based on the co-assembly of L-glutamic acid lipid (LG/Nico) and cobalt ions exhibited excellent photocatalytic CO2 reduction, with 208 724 µmol g-1 CO production within 24 h and 90 % CO/H2 selectivity, or 166 826 µmol g-1 CO production within 12 h and 46 % CO/H2 selectivity, depending on the water content of the solvent. The alkyl chains of LG/Nico provide a hydrophobic microenvironment for efficient gas transfer, and the assembled bilayers induce a synergistic effect between two adjacent Co ions for catalyzing the CO2 reduction reaction. These architectures present new alternatives for the development of highly efficient photocatalytic soft matter based on the assembly of small amphiphilic molecules.

Mesoporous Polyimide-Linked Covalent Organic Framework with Multiple Redox-Active Sites for High-Performance Cathodic Li Storage.

Covalent organic frameworks (COFs) are gaining increasing attention as renewable cathode materials for Li-ion batteries. However, COF electrodes reported so far still exhibit unsatisfying capacity due to their limited active site density and insufficient utilization. Herein, a new two-dimensional polyimide-linked COF, HATN-AQ-COF with multiple redox-active sites for storing Li+ ions, was designed and fabricated from a new module of 2,3,8,9,14,15-hexacarboxyl hexaazatrinaphthalene trianhydrides with a 2,6-diaminoanthraquinone linker. HATN-AQ-COF possessing excellent stability, good conductivity, and a large pore size of 3.8 nm enables the stable and fast ion transport. This, in combination with the abundant redox active sites, results in a high reversible capacity of 319 mAh g-1 at 0.5 C (1 C=358 mA g-1 ) for the HATN-AQ-COF electrode with a high active site utilization of 89 % and good cycle performance, representing one of the best performances among the reported COF electrodes.

Two-Dimensional Covalent Organic Frameworks with Cobalt(II)-Phthalocyanine Sites for Efficient Electrocatalytic Carbon Dioxide Reduction.

The rapid development in synthesis methodology and applications for covalent organic frameworks (COFs) has been witnessed in recent years. However, the synthesis of highly stable functional COFs still remains a great challenge. Herein two-dimensional polyimide-linked phthalocyanine COFs (denoted as CoPc-PI-COF-1 and CoPc-PI-COF-2) have been devised and prepared through the solvothermal reaction of the tetraanhydrides of 2,3,9,10,16,17,23,24-octacarboxyphthalocyaninato cobalt(II) with 1,4-phenylenediamine and 4,4'-biphenyldiamine, respectively. The resultant CoPc-PI-COFs with a four-connected sql net exhibit AA stacking configurations according to powder X-ray diffraction studies, showing permanent porosity, thermal stability above 300 °C, and excellent resistance to a 12 M HCl aqueous solution for 20 days. Current-voltage curves reveal the conductivity of CoPc-PI-COF-1 and CoPc-PI-COF-2 with the value of 3.7 × 10-3 and 1.6 × 10-3 S m-1, respectively. Due to the same Co(II) electroactive sites together with similar permanent porosity and CO2 adsorption capacity for CoPc-PI-COFs, the cathodes made up of COFs and carbon black display a similar CO2-to-CO Faradaic efficiency of 87-97% at applied potentials between -0.60 and -0.90 V (vs RHE) in 0.5 M KHCO3 solution. However, in comparison with the CoPc-PI-COF-2&carbon black electrode, the CoPc-PI-COF-1 counterpart provides a larger current density (jCO) of -21.2 mA cm-2 at -0.90 V associated with its higher conductivity. This cathode also has a high turnover number and turnover frequency, amounting to 277 000 and 2.2 s-1 at -0.70 V during 40 h of measurement. The present result clearly discloses the great potential of 2D porous crystalline solids in electrocatalysis.

Multipolar Porphyrin-Triazatruxene Arrays for Two-Photon Fluorescence Cell Imaging.

Two-photon excited fluorescent (TPEF) materials are highly desirable for bioimaging applications owing to their unique characteristics of deep-tissue penetration and high spatiotemporal resolution. Herein, by connecting one, two, or three electron-deficient zinc porphyrin units to an electron-rich triazatruxene core via ethynyl π-bridges, conjugated multipolar molecules TAT-(ZnP)n (n=1-3) were developed as TPEF materials for cell imaging. The three new dyes present high fluorescence quantum yields (0.40-0.47) and rationally improved two-photon absorption (TPA) properties. In particular, the peak TPA cross section of TAT-ZnP (436 GM) is significantly larger than that of the ZnP reference (59 GM). The δTPA values of TAT-(ZnP)2 and TAT-(ZnP)3 further increase to 1031 and up to 1496 GM, respectively, indicating the effect of incorporated ZnP units on the TPA properties. The substantial improvement of the TPEF properties is attributed to the formation of π-conjugated quadrapole/octupole molecules and the extension of D-π-A-D systems, which has been rationalized by density function theory (DFT) calculations. Moreover, all of the three new dyes display good biocompatibility and preferential targeting ability toward cytomembrane, thus can be superior candidates for TPEF imaging of living cells. Overall, this work demonstrated a promising strategy for the development of porphyrin-based TPEF materials by the construction and extension of D-π-A-D multipolar array.

Compartmentalization within Nanofibers of Double-Decker Phthalocyanine Induces High-Performance Sensing in both Aqueous Solution and the Gas Phase.

The functionalization of natural 1D architectures is dependent on hierarchically inner nanostructures. However, the artificial supramolecular nanofibers or nanotubes were rarely developed with complex inner structures. Inspired by a biomimetic strategy, single-molecule-diameter nanofibers of double-decker phthalocyanine (EuPc2) with compartmentalized internal space and fantastic electrochemical features were developed upon air/water interfacial assembly with poly-l-lysine. EuPc2/poly-l-lysine nanofibers can be electrochemical sensors both in water and the gas phase and have the best analytical performances for nitrite among all the porphyrins or phthalocyanines monomers and assemblies. Imbedding nitrite in compartments not only promotes the sensing but also changes the supramolecular chirality of nanofibers, and the morphological-dependent sensing properties of EuPc2 assemblies in water are different from that in the gas phase. These results suggest the unprecedented properties for diverse applications of artificial 1D architectures containing complex inner nanostructures.

Bis[1,8,15,22-tetrakis(3-pentyloxy)phthalocyaninato]terbium Double-Decker Single-Ion Magnets.

For the purpose of further exploring the effect of nonperipherally attached substituents on single-ion magnet (SIMs) performance, tetrasubstituted bis[1,8,15,22-tetrakis(3-pentyloxy)phthalocyaninato]terbium double-deckers, in both the reduced form TbH[Pc(α-OC5H11)4]2 (1) and the neutral form Tb[Pc(α-OC5H11)4]2 (2), were prepared. Single-crystal X-ray diffraction analysis for 2 unambiguously demonstrates the pinwheellike molecular structure with C4 symmetry. Magnetic investigations of the two bis(phthalocyaninato)terbium double-deckers reveal their characteristic SIM nature. 2 exhibits SIM performance superior to that of 1, as revealed by the larger energy barrier of 466 K for the former species and 431 K for the latter species due to the presence of organic radical-f (radical-Tb) interactions. The enhanced SIM performance of 2 in comparison to 1 actually stems from the presence of radical-f interactions and an enhanced ligand field strength. The latter positive factor is indicated by the electrostatic potential around the terbium ion on the basis of density functional theory (DFT) calculations.

Fabricating Bis(phthalocyaninato) Terbium SIM into Tetrakis(phthalocyaninato) Terbium SMM with Enhanced Performance through Sodium Coordination.

The non-peripherally substituted 1,4,8,11,15,18,22,25-octa(butoxy)-phthalocyanine-involved unsymmetrical heteroleptic bis(phthalocyaninato) terbium double-decker, Tb(Pc){H[Pc(α-OC4 H9 )8 ]} (Pc=unsubstituted phthalocyanine) (1), was revealed to exhibit typical single ion magnet (SIM) behavior with effective energy barrier, 180 K (125 cm-1 ), and blocking temperature, 2 K, due to the severe deviation of the terbium coordination polyhedron from square-antiprismatic geometry. Fabrication of this double-decker compound into the novel tetrakis(phthalocyaninato) terbium pseudo-quadruple-decker Na2 {Tb(Pc)[Pc(α-OC4 H9 )8 ]}2 (2) single molecule magnet (SMM) not only optimizes the coordination polyhedron of terbium ion towards the square-antiprismatic geometry and intensifies the coordination field strength, but more importantly significantly enhances the molecular magnetic anisotropy in the unsymmetrical bis(phthalocyaninato) double-decker unit, along with the change of the counter cation from H+ of 1 to Na+ of 2, leading to an significantly enhanced magnetic behavior with spin-reversal energy barrier, 528 K (367 cm-1 ), and blocking temperature, 25 K. The present result is surely helpful towards developing novel tetrapyrrole lanthanide SMMs through rational design and self-assembly from bis(tetrapyrrole) lanthanide single ion magnet (SIM) building block.

Hemiporphyrazine-Involved Sandwich Dysprosium Double-Decker Single-Ion Magnets.

Both heteroleptic (phthalocyaninato)(hemiporphyrazinato) and homoleptic bis(hemiporphyrazinato) dysprosium double-decker complexes, Dy[H(Hp)2] (1) and Dy[H(Pc)(Hp)] (2) (H2Pc = metal-free phthalocyanine; H2Hp = metal-free hemiporphyrazine), were designed, synthesized, and structurally characterized. The dysprosium center in both double-deckers are octa-coordinated with a nearly ideal square-antiprismatic coordination geometry, which provides an increased molecular anisotropy for the dysprosium ion and ensures the strengthened magnetic properties of both single-ion magnets (SIMs) in terms of coordination geometry. Magnetic studies reveal that both double-deckers exhibit typical SIM behavior with a spin reversal energy barrier of 80.1 ± 6.3 K for 1 and 57.3 ± 3.8 K for 2 as well as the hysteresis loops emerging at 3 K. In particular, introduction of two Hp ligands with four pyridine nitrogen atoms coordinated with the dysprosium spin center endows Dy[H(Hp)2] (1) with the thus far highest energy barrier among the sandwich-type dysprosium SIMs with N4-macrocyclic ligands, revealing the potential applications of sandwich-type lanthanide complexes with Hp ligands in molecular-based information storage.

Two-Photon Excited FRET Dyads for Lysosome-Targeted Imaging and Photodynamic Therapy.

Two-photon excitable fluorescent dyes with integrated functions of targeted imaging and photodynamic therapy (PDT) are highly desired for the development of cancer theranostic agents. Herein, fluorescence resonance energy transfer (FRET) dyads, AceDAN-H2Por-Lyso (1a) and AceDAN-ZnPor-Lyso (1b), were developed for two-photon excited (TPE) lysosome-targeted fluorescence imaging and PDT of cancer cells. Under one-photon or two-photon excitation, the AceDAN donor can effectively transfer the excited state energy to the porphyrin acceptor via high efficient FRET, leading to the generation of deep-red fluorescence and singlet oxygen for cell imaging and PDT, respectively. 1a and 1b exhibit high photocytotoxicity and low dark cytotoxicity, in addition to strong lysosomal targeting capability in living cells. By taking the advantages of the two-photon absorption properties of the AceDAN donor and the properly distributed S1 and T1 states of the porphyrin acceptor, the AceDAN-porphyrin dyads 1a and 1b have been successfully applied to TPE-fluorescence imaging for tracking the significant morphology changes of cancer cells under two-photon laser irradiation.

Mixed Phthalocyanine-Porphyrin Fused Conjugated Pentameric Nanoarrays.

The largest phthalocyanine-porphyrin-fused pentameric molecular arrays have been synthesized and spectroscopically characterized. The saddled molecular conformation revealed for the pentamer by DFT-D3 calculation in combination with the bulky peripheral substituents precludes effective face-to-face π-π intermolecular interaction. As a consequence, intermolecular C-H⋅⋅⋅π interactions together with the ubiquitous dispersion force arrays help to self-assemble the representative metal-free pentameric molecules into the three-dimensional supramolecular structures with nanorod morphology in CHCl3 and n-butanol. Powder X-ray diffraction (XRD) analysis and selected area electron diffraction (SAED) disclose the gradually increased long range of molecular ordering in the nanorods along with the increase in the substrate temperature from 30, 40, 50, to 60 °C. This in turn results in an increase in the semiconductivity of the single nanorod in the same order from 9.4×10-9 to 3.8×10-8 , 7.6×10-7 , and 6.3×10-5  S m-1 .