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Two-Dimensional Chemiresistive Covalent Organic Framework with 8 High Intrinsic Conductivity 9 10 Zheng Meng,1 Robert M

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Two-Dimensional Chemiresistive Covalent Organic Framework with 8 High Intrinsic Conductivity 9 10 Zheng Meng,1 Robert M Page 1 of 11 Journal of the American Chemical Society 1 2 3 4 5 6 7 Two-Dimensional Chemiresistive Covalent Organic Framework with 8 High Intrinsic Conductivity 9 10 Zheng Meng,1 Robert M. Stolz,1 Katherine A. Mirica*1 11 12 1Department of Chemistry, Burke Laboratory, Dartmouth College, Hanover, New Hampshire, 03755 13 14 15 16 Supporting Information Placeholder 17 18 ABSTRACT: This paper describes the synthesis of a novel intrinsically conductive two-dimensional (2D) covalent organic 19 framework (COF) through the aromatic annulation of 2,3,9,10,16,17,23,24-octa-aminophthalocyanine nickel(II) and pyrene- 20 4,5,9,10-tetraone. The intrinsic bulk conductivity of the COF material (termed COF-DC-8) reached 2.5110-3 S/m, and increased 21 by three orders of magnitude with I2 doping. Electronic calculations revealed an anisotropic band structure, with the possibility 22 for significant contribution from out-of-plane charge-transport to the intrinsic bulk conductivity. Upon integration into 23 chemiresistive devices, this conductive COF showed excellent responses to various reducing and oxidizing gases, including NH3, 24 H2S, NO, and NO2, with parts-per-billion (ppb) level of limits of detection (LOD for NH3=70 ppb, for H2S=204 ppb, for NO=5 25 ppb, and for NO2=16 ppb based on 1.5 min exposure). Electron paramagnetic resonance spectroscopy and X-ray photoelectron 26 spectroscopy studies suggested that the chemiresistive response of the COF-DC-8 involves charge transfer interactions 27 between the analyte and nickelphthalocyanine component of the framework. 28 29 30 INTRODUCTION molecular solids,11 and conductive coordination polymers),5b, 31 5c, 12 the strategy for maximizing the intrinsic bulk 32 The development of chemically robust, porous, and conductivity of COFs can leverage through-bond and 33 electrically conductive nanomaterials drives progress in 1 2 3 through-space charge transport characteristics. To achieve 34 electronic devices, energy storage, catalysis, and chemical 4 through-bond charge transport, the covalent linkages 35 sensing. Recent advances in the synthesis of electrically formed during COF synthesis must promote efficient charge 36 conductive metal−organic frameworks (MOFs) have enabled delocalization. Previous studies on 1D and 2D conjugated 37 a range of applications in electrocatalysis, energy storage, and chemical sensing that were previously inaccessible using polymers with single bonds in their backbones rarely showed 38 13 5 high charge carrier mobility values, suggesting that borate 39 traditionally insulating MOFs. Both through-bond and 40 through-space charge transport mechanisms have proven to 5 41 be effective in promoting conductivity in MOFs. In 42 particular, the molecular design strategy focusing on planar 43 two-dimensional MOFs, in which the formation of π–d 44 conjugated sheets can promote the delocalization of charge, 6 45 has yielded metallic conductivities. Despite progress in the 46 development of conductive MOFs, the design and synthesis 47 of electrically conductive π–conjugated covalent organic 48 frameworks (COFs) connected by chemically robust bonds— 49 which arguably possess superior chemical stability to 50 frameworks derived from reversible coordination chemistry 51 and borate or Schiff-base chemistry —has remained a 7 52 tremendous challenge. Although doping of COFs with 53 oxidants and guest molecules has led to conductivities of -2 -1 8 54 ~10 to 10 S/m, access to intrinsically conductive COFs 9 55 with high bulk conductivity remains limited. 56 Capitalizing on the general principles of molecular 57 engineering for other classes of conductive materials (e.g., 58 conductive organic polymers,10 conductive organic 59 60 ACS Paragon Plus Environment Journal of the American Chemical Society Page 2 of 11 building blocks: octaamino-derived nickelphthalocyanine 1 (NiOAPc) and pyrenetetraone (TOPyr). The annulation of 2 tetraketone and octaamine precursors to form pyrazine rings 3 generates a fully aromatic conjugated framework structure 4 with square apertures (Scheme 1). The utilization of the 5 nickelphthalocyanine core was inspired by its application in 6 the construction of conductive frameworks materials 7 demonstrated by our group18 and others,3d, 19 as well as its 8 affinity to small gaseous analytes.20 The resulting fully 9 conjugated 2D lattice with Lieb topology can maximize 10 through-bond charge delocalization, while the stacking of 11 the embedded metallophthalocyanine units confined within 12 the rigid framework material can efficiently promote out-of- 13 plane charge transfer. The bulk conductivity—which 14 characterizes the weighted average of contributions from 15 through-bond and through-space charge delocalization in 16 polycrystalline COF-DC-8—reached 2.5110-3 S/m, 17 representing the highest bulk conductivity achieved within 18 an intrinsically conductive COF. 19 Chemiresistive devices made from this conductive COF 20 showed excellent responses and ultra-low limits of detection 21 for gaseous analytes (1.5 min exposure-based LODs: 70 ppb 22 for NH , 204 ppb for H S, 5 ppb for NO, and 16 ppb for NO ). 23 3 2 2 Increases in resistance towards reducing gases and 24 decreases in resistance towards oxidizing gases were 25 consistent with p-type semiconductive character of the COF. 26 Spectroscopic characterization using electron paramagnetic 27 resonance (EPR) and X-ray photoelectron spectroscopy (XPS) 28 suggested that the chemiresistivite response of COF-DC-8 29 Scheme 1. The synthetic route for 2D conductive COF-DC-8 originates from the combination of binding and charge 30 with nickelphthalocyanine and pyrene subunits connected transfer interactions between the analyte and the Ni- 31 by pyrazine rings. containing phthalocyanine component of the framework. 32 The promising chemiresistive performance highlights the 33 and imine linkages in typical COFs may be inefficient at potential application of this modular class of materials in the 34 facilitating through-bond charge transport. While full fabrication of electronic devices and chemical sensors. 35 annulation of building blocks through aromatic linkages has 36 been established as a promising strategy for conjugated 2D RESULTS AND DISCUSSION 37 COF formation,7e, 13c, 14 it has not yet yielded materials with Synthesis and Characterization. As drawn in Scheme 38 high intrinsic conductivities. Interestingly, recent studies 1, the condensation reaction performed in a mixed solvent 39 highlighted the unique role of topology in enhancing of dimethylacetamide (DMAC) and o-diclorobenzene (DCB) 40 through-bond charge delocalization in conjugated 2D COFs, in the presence of sulfuric acid for 10 days gave the desired 41 with Lieb lattice15 being more favorable over Kagome COF-DC-8 as a dark green powder (see Section 2.2 in 42 lattice.16 A complementary strategy for achieving through- Supporting Information for details). Microwave heating 43 space transport requires maximizing orbital interactions significantly reduced the reaction time to 10 hours, albeit at 44 within the resulting layered framework structure through the expense of slightly diminished crystallinity (entry 10 in 45 strategic choice of building blocks. Although several reports Table S1 and Figure S6). Efforts to optimize reaction 46 have taken advantage of π-stacking for designing COF- conditions yielded several alternative approaches for 47 based materials with reasonable charge carrier mobilities (8.1 accessing COF-DC-8, including the use of the aqueous 48 cm2 V1 s1),7c, 17 their bulk conductivities remained limited. solution of acetic acid in a mixed solvent system of DMAC 49 We reasoned that by simultaneously capitalizing on both and DCB (entry 14 in Table S1 and Figure S6), and the use 50 molecular design strategies of through-bond and through- of NMP as the solvent in the presence of sulfuric acid or 51 space transport in a highly planar, two-dimensional, fully aqueous solution of acetic acid (entry 17, 18 in Table S1 and 52 conjugated material based on a Lieb lattice may lead to the Figure S6). 53 realization of a high intrinsic bulk electrical conductivity 54 within a COF-based material. Fourier-transform infrared spectroscopy of COF-DC-8 (Figure S7) showed the appearance of characteristic 55 This paper describes the development of a novel absorption bands of the phenazine system at 1518, 1431, 56 intrinsically conductive COF (COF-DC-8) through the and 1351 cm–1, while absorption bands of C=O and –NH 57 condensation reaction between the highly planar conjugated 2 58 59 60 ACS Paragon Plus Environment Page 3 of 11 Journal of the American Chemical Society groups from NiOAPc and TOPyr were absent, indicating the peaks were observed at 2θ = 4.06°, 8.19°, 11.48°, 12.26°, and 1 formation of phenazine linkages. XPS showed characteristic 26.65°, that were assigned to the [100], [200], [220], [300], 2 bands for the K-edge of carbon (285.9 eV) and nitrogen and [001] facets, respectively (Figure 1b). Although PXRD 3 (398.6 eV) in C=N bond (Figure S9), indicating the presence displayed peak broadening which was possibly due to small 4 of sp2-hybridized nitrogen atoms. Elemental analysis showed crystallite size, the peak intensity and position were sufficient 5 that C:N:Ni ratios were consistent with theoretical values for confirming the framework structure and key cell 6 (Table S2), although the absolute percentages of C, N, and parameters of DC-COF-8. The strong diffractions from the 7 Ni were slightly lower than theoretical values. The [100] and [200] facets indicated long-range order within the 8 discrepancy between the theoretical and observed values ab plane of the structure. The Ni-to-Ni distance on the side 9 could be from the existence of unreacted C=O and NH2 of the square, based on those two diffractions, was 10 groups at sheet edges7d and the entrapment of small- calculated to be 2.17 nm. The presence of the [001] facet at 11 molecule volatiles (acetone, H2O, or DMAC) included in the 26.65° suggested the structural ordering with a 3.34 Å 12 pores, as suggested by XPS (Figure S9 in section 4) and separation of layers along the c axis perpendicular to the 2D 13 thermal gravimetric analysis (see Figure S20 in section 10) sheets.
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