Supporting Information File for. Design of van der Waals Two-Dimensional Heterostructures from

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1 Supporting Information File for Design of van der Waals Two-Dimensional Heterostructures from Facially Polarized Janus all-cis 1,2,3,4,5,6-hexafluorocyclohexane (C 6 H 6 F 6 ) Saied Md Pratik, 1 A. Nijamudheen, 2 Ayan Datta 1 * 1 Department of Spectroscopy, Indian Association for the Cultivation of Science, Jadavpur , West Bengal (India), 2 Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, NY * spad@iacs.res.in Contents 1. Figure S1: HOMO and LUMO plots for 1-X, 1-Y and X-1-Y complexes. 2. Details of NCIPLOT calculations and Figure S2: Reduced density gradient (s) vs sign(λ2)ρ plot using NCIPLOT program for 1-X, 1-Y and X-1-Y complexes. 3. Figure S3: Band structure of Hydroflourinated graphene (HFG) monolayer using GGA-PBE functional. 4. Figure S4: Calculated total density of states (TDOS) and partial density of states (PDOS) for HFG-graphane bilayer using GGA-PBE functional. 5. Figure S5: Band structure of HFG-graphene and graphene-hfg-graphane heterostructures using GGA-PBE functional. S1

2 6. Cartesian Coordinates for the optimized structures, their zero point energy corrected total energies in Hartree and low frequencies calculated at M06/6-31+G(d,p) level of theory in the gas phase. Harmonic Frequencies calculated at 298K. 7. Complete Reference for Gaussian 09 and Amsterdam Density Functional Theory (ADF) software package. 1. Figure S1: HOMO and LUMO plots for 1-X, 1-Y and X-1-Y complexes. S2

3 Figure S1: The HOMO and HUMO plot for 1-benzene, 1-pyrene, 1-cyclohexane, 1- perhydropyrene, benzene-1-cyclohexane and pyrene-1-perhydropyrene. 2. Details of NCIPLOT calculations: The nature of dispersion interactions between the 1-X, 1-Y and X-1-Y are demonstrated by NCIPLOT analysis. This provides a simple distinction between attractive and repulsive domains of Non-Covalent Interactions. The 2D-plot produce by NCIPLOT, contains the reduce electron density gradient (s) and electron density values (ρ). The s and ρ are connected by the following relations 1 = 2(3 ) The stabilization or destabilization interactions arise in the complexes can be determined from the sign of 2 ρ at critical bonding points. The negative sign of 2 ρ indicates net gradient flux of electron density is localized (stabilizing interaction) whereas the positive sign indicates the net gradient flux of electron density is diminishing (destabilizing interaction). To obtained the NCIPLOT from DFT wave functions, the reduced density gradient (RDG) s(r) have to be plotted onto the sign(λ 2 )ρ(r). Herein, λ 2 (second eigenvalue of the electron density Hessian matrix) is represented as 2 ρ =λ 1 + λ 2 + λ 3 (where, λ 1 < λ 2 < λ 3 ). λ 3 varies along inter-nuclear distance whereas, λ 1 and λ 2 vary along the normal to the λ 3 eigenvector. Depending on the nature of interactions λ 2 can be negative or positive. The negative of λ 2 indicates stabilizing while the positive indicates destabilizing interactions. Hence, by analyzing the sign of λ 2 one can distinguish the attractive (stabilizing) or repulsive (destabilizing) interactions. These plots are S3

4 obtained from M06 functional and reduced gradient on cuboids grids, with a 0.1 au step size for each complex. Figure S2: Reduced density gradient (s) vs sign(λ2)ρ plot using NCIPLOT program for 1-X, 1-Y and X-1-Y complexes. Figure S2: Reduced density gradient (s) vs sign(λ2)ρ plot using NCIPLOT program for (a) 1- benzene, (b) 1-pyrene, (c) 1-coronene, (d) 1-cyclohexane, (e) 1-perhydropyrene, (f) 1- perhydrocoronene, (g) benzene-1-cyclohexane, (h) pyrene-1-perhydropyrene and (i) coronene-1- perhydrocoronene. S4

5 3. Figure S3: Band structure of Hydroflourinated graphene (HFG) monolayer. Figure S3: Calculated band structure of Hydroflourinated graphene (HFG) monolayer using GGA-PBE functional. 4. Figure S4: Total density of states (TDOS) and partial density of states (PDOS) for HFGgraphane bilayer. S5

6 Figure S4: Calculated total density of states (TDOS) HFG-graphane bilayer (black line) and partial density of states (PDOS) of graphane (red line) and HFG (green line), respectively. and partial density of states. 5. Figure S5: Band structure of HFG-graphene and graphene-hfg-graphane heterostructures using GGA-PBE functional. (a) (b) Figure S5: Calculated band structure of (a) HFG-graphene (b) graphene-hfg-graphane heterostructures. The energy is scaled with respect to Fermi level. 6. Cartesian Coordinates for the optimized structures, their zero point energy corrected total energies in Hartree and low frequencies calculated at M06/6-31+G(d,p) level of theory in the gas phase. Harmonic Frequencies calculated at 298K. (a) 1-benzene Center Atomic Coordinates (Angstroms) Number Number X Y Z S6

7 ENERGY= Hartree Frequencies (b) 1-pyrene Center Atomic Coordinates (Angstroms) Number Number X Y Z S7

8 ENERGY= Hartree Frequencies S8

9 (c) 1-coronene Center Atomic Coordinates (Angstroms) Number Number X Y Z S9

10 ENERGY= Hartree Frequencies (d) 1-Cyclohexane Center Atomic Coordinates (Angstroms) Number Number X Y Z S10

11 ENERGY= Hartree Frequencies (e) 1-perhydropyrene Center Atomic Coordinates (Angstroms) Number Number X Y Z S11

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13 ENERGY= Hartree Frequencies (f) 1-perhydrocoronene Center Atomic Coordinates (Angstroms) Number Number X Y Z S13

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15 ENERGY= Hartree Frequencies (g) benzene-1-cyclohexane Center Atomic Coordinates (Angstroms) Number Number X Y Z S15

16 ENERGY= Hartree Frequencies (h) pyrene-1-perhydropyrene Center Atomic Coordinates (Angstroms) Number Number X Y Z S16

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18 ENERGY= Hartree Frequencies (i) coronene-1-perhydrocoronene Center Atomic Coordinates (Angstroms) Number Number X Y Z S18

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21 ENERGY= Hartree Frequencies Complete Reference for Gaussian 09 and Amsterdam Density Functional Theory (ADF) software package. (i) Complete Reference for Gaussian 09: Gaussian 09, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G.E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.;Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.;Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, Jr., J. A.;Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, N. J.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, Ö.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian, Inc., Wallingford CT, (ii). Complete Reference for Amsterdam Density Functional software (ADF): ADF , SCM, Theoretical Chemistry, Vrije Universiteit, Amsterdam, The Netherlands. E.J. Baerends, J. Autschbach, A. Bérces, F.M. Bickelhaupt, C.Bo, P.M. Boerrigter, L. Cavallo, D.P. Chong, L. Deng, R.M. Dickson, D.E. Ellis, M. van Faassen, L. Fan, T. H. Fischer, C.Fonseca Guerra, S.J.A. van Gisbergen, A.W. Götz, J.A. Groeneveld, O.V. Gritsenko, M. Grüning, F.E. Harris, P. van den Hoek, C.R. Jacob, H. Jacobsen, L. Jensen, G. van Kessel, F. Kootstra, M.V. Krykunov, E. van Lenthe, D.A. McCormack, A. Michalak, J. Neugebauer, V.P. Nicu, V.P. Osinga, S. Patchkovskii, P.H.T. Philipsen, D. Post, C.C. Pye, W. Ravenek, J.I. Rodríguez, P. Ros, P.R.T. Schipper, G. Schreckenbach,J.G. Snijders, M. Solà, M. Swart, D. Swerhone, G. te Velde, P. Vernooijs, L. Versluis, L. Visscher, O. Visser, F. Wang, T.A.Wesolowski, E.M. van Wezenbeek, G. Wiesenekker, S.K. Wolff, T.K. Woo, A.L. Yakovlev, and T. Ziegler S21