Synthesis of mesoscale ordered two-dimensional π-conjugated polymers with semiconducting properties

Galeotti, Gianluca; Marchi, Fabrizio De; Hamzehpoor, Ehsan; MacLean, Oliver; Rao, M. Rajeswara; Chen, Yulan; Besteiro, Lucas V.; Dettmann, Dominik; Ferrari, L.; Frezza, Federico; Sheverdyaeva, P. M.; Liu, R.; Kundu, Asish K.; Moras, Paolo; Ebrahimi, Maryam; Gallagher, M. C.; Rosei, Federico; Perepichka, Dmitrii F.; Contini, G.

doi:10.1038/s41563-020-0682-z

Cited by 193 publications

(231 citation statements)

References 52 publications

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“…provided the first example of a 2D Au‐based CP with Dirac cones and flat bands. [ 18 ] This seminal work is a nice proof of concept demonstrating the possibility of achieving domain dimensions >100 × 100 nm 2 on a super smooth Au (111) substrate. Yet, achieving large highly ordered domains of 2D CPs with observed Dirac cones, metallicity, and flat bands based on cheaper metal centers such as Ni and Cu as well as their fabrication on inexpensive substrates such as glass or Si wafer are highly desirable.…”

Section: Introductionmentioning

confidence: 99%

Semiconducting to Metallic Electronic Landscapes in Defects‐Controlled 2D π‐d Conjugated Coordination Polymer Thin Films

Ogle

Lahiri

Jaye

et al. 2020

Adv Funct Materials

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Two‐dimensional coordination polymers (2DCPs) have been predicted to exhibit exotic properties such as superconductivity, topological insulating behavior, catalytic activity, and superior ion transport for energy applications; experimentally, these materials have fallen short of their expectation due to the lack of synthesis protocols that yield continuous, large crystallite domains, and highly ordered thin films with controllable physical and chemical properties. Herein, the fabrication of large‐area, highly ordered 2DCP thin films with large crystallite domains using chemical vapor deposition (CVD) approaches is described. It is demonstrated that defects and the packing motifs of 2DCP thin films may be controlled by adjusting the vapor–vapor and vapor–solid interactions of the metal and organic linker precursors during the CVD fabrication process. Such control allows for the fabrication of defects‐controlled 2DCP thin films that show either semiconducting or metallic behavior. The findings provide the first demonstration of tuning the electrical properties of sub 100 nm‐thick continuous 2DCP thin films by controlling their electronic landscape through defect engineering. As such, it is determined that large‐area, highly ordered 2DCP thin films may undergo a semiconducting to metallic transition that is correlated to changes in morphology, crystalline domain sizes, crystallite orientation, defect interactions, and electronic structure.

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Section: Introductionmentioning

confidence: 99%

Semiconducting to Metallic Electronic Landscapes in Defects‐Controlled 2D π‐d Conjugated Coordination Polymer Thin Films

Ogle

Lahiri

Jaye

et al. 2020

Adv Funct Materials

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“…In the last decades, a great effort, both from the fundamental research and technological application point of view, has been made to exploit organic–metal interfaces in the engineering of functional molecular‐based spintronics devices [1–4] . Among others, planar and aromatic metalorganic molecules, such as metal‐phthalocyanines (MPcs), metal‐porphyrins (MPs) and their derivatives, have been widely employed in molecular spintronics because they may manifest a broad variety of spin‐related phenomena, ranging from magnetic anisotropy [5, 6] to the Kondo effect [7] .…”

Section: Introductionmentioning

confidence: 99%

Ferrous to Ferric Transition in Fe‐Phthalocyanine Driven by NO₂ Exposure

Cojocariu

Carlotto

Sturmeit

et al. 2021

Chemistry A European J

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Due to its unique magnetic properties offered by the open‐shell electronic structure of the central metal ion, and for being an effective catalyst in a wide variety of reactions, iron phthalocyanine has drawn significant interest from the scientific community. Nevertheless, upon surface deposition, the magnetic properties of the molecular layer can be significantly affected by the coupling occurring at the interface, and the more reactive the surface, the stronger is the impact on the spin state. Here, we show that on Cu(100), indeed, the strong hybridization between the Fe d‐states of FePc and the sp‐band of the copper substrate modifies the charge distribution in the molecule, significantly influencing the magnetic properties of the iron ion. The FeII ion is stabilized in the low singlet spin state (S=0), leading to the complete quenching of the molecule magnetic moment. By exploiting the FePc/Cu(100) interface, we demonstrate that NO2 dissociation can be used to gradually change the magnetic properties of the iron ion, by trimming the gas dosage. For lower doses, the FePc film is decoupled from the copper substrate, restoring the gas phase triplet spin state (S=1). A higher dose induces the transition from ferrous to ferric phthalocyanine, in its intermediate spin state, with enhanced magnetic moment due to the interaction with the atomic ligands. Remarkably, in this way, three different spin configurations have been observed within the same metalorganic/metal interface by exposing it to different doses of NO2 at room temperature.

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“…[9] Therefore, structurally defined 2D CPs with p-electron delocalization in two dimensions are expected to offer highly desirable properties for organic optoelectronics, such as an ideal band structure for superior charge carrier mobility, tailorable highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) band gaps, and defect tolerance enabled by increased dimensionality in comparison to that of linear conjugated polymers. [10] In contrast to the emergent 2D p-conjugated covalent organic frameworks (COFs), which can be regarded as 2D CPs and have thus far been dominated by Schiff base reactions, [11] the synthesis of 2D CPs with fully sp 2 -carbonlinked backbones still lacks effective protocols to generate crystalline polymer materials. [12] In particular, sp 2 -carbonlinked (or vinylene-linked) 2D CPs provide high chemical and thermal stabilities as well as complete p-conjugation over the whole 2D polymer framework, making these materials highly attractive for various applications, such as in optoelectronics, spintronics, and energy storage.…”

mentioning

confidence: 99%

Synthesis of Vinylene‐Linked Two‐Dimensional Conjugated Polymers via the Horner–Wadsworth–Emmons Reaction

et al. 2020

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In this work, we demonstrate the first synthesis of vinylene‐linked 2D CPs, namely, 2D poly(phenylenequinoxalinevinylene)s 2D‐PPQV1 and 2D‐PPQV2, via the Horner–Wadsworth–Emmons (HWE) reaction of C2‐symmetric 1,4‐bis(diethylphosphonomethyl)benzene or 4,4′‐bis(diethylphosphonomethyl)biphenyl with C3‐symmetric 2,3,8,9,14,15‐hexa(4‐formylphenyl)diquinoxalino[2,3‐a:2′,3′‐c]phenazine as monomers. Density functional theory (DFT) simulations unveil the crucial role of the initial reversible C−C single bond formation for the synthesis of crystalline 2D CPs. Powder X‐ray diffraction (PXRD) studies and nitrogen adsorption‐desorption measurements demonstrate the formation of proclaimed crystalline, dual‐pore structures with surface areas of up to 440 m2 g−1. More importantly, the optoelectronic properties of the obtained 2D‐PPQV1 (Eg=2.2 eV) and 2D‐PPQV2 (Eg=2.2 eV) are compared with those of cyano‐vinylene‐linked 2D‐CN‐PPQV1 (Eg=2.4 eV) produced by the Knoevenagel reaction and imine‐linked 2D COF analog (2D‐C=N‐PPQV1, Eg=2.3 eV), unambiguously proving the superior conjugation of the vinylene‐linked 2D CPs using the HWE reaction.

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Synthesis of mesoscale ordered two-dimensional π-conjugated polymers with semiconducting properties

Cited by 193 publications

References 52 publications

Semiconducting to Metallic Electronic Landscapes in Defects‐Controlled 2D π‐d Conjugated Coordination Polymer Thin Films

Semiconducting to Metallic Electronic Landscapes in Defects‐Controlled 2D π‐d Conjugated Coordination Polymer Thin Films

Ferrous to Ferric Transition in Fe‐Phthalocyanine Driven by NO₂ Exposure

Synthesis of Vinylene‐Linked Two‐Dimensional Conjugated Polymers via the Horner–Wadsworth–Emmons Reaction

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Synthesis of mesoscale ordered two-dimensional π-conjugated polymers with semiconducting properties

Cited by 193 publications

References 52 publications

Semiconducting to Metallic Electronic Landscapes in Defects‐Controlled 2D π‐d Conjugated Coordination Polymer Thin Films

Semiconducting to Metallic Electronic Landscapes in Defects‐Controlled 2D π‐d Conjugated Coordination Polymer Thin Films

Ferrous to Ferric Transition in Fe‐Phthalocyanine Driven by NO2 Exposure

Synthesis of Vinylene‐Linked Two‐Dimensional Conjugated Polymers via the Horner–Wadsworth–Emmons Reaction

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Ferrous to Ferric Transition in Fe‐Phthalocyanine Driven by NO₂ Exposure