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Supplementary material

Synthesis and compound identification

Solutions of 1-naphthylmagnesium bromide (1) and 2-naphthylmagnesium bromide (3) were prepared in tetrahydrofuran (THF) according to previously published procedures [10]. The solution of (1) or (3) was cooled and D2O in anhydrous THF was added slowly in 30 min. The mixture was stirred for 10 hours at room temperature. The crude products (2) and (4) were purified by column chromatography.

The products were identified and characterized by the following physical data:

1-D-naphthalene (2):

H1 NMR (CDCl3, 300K): δ = 7.97-7.91 (m, 3H), 7.61-7.54 (m, 4H).

C13 NMR (CDCl3, 300K): δ = 125.7, 125.8, 127.7, 127.8, 133.3, 133.4.

GC-MS m/z (rel. int.): 129 (M+, 100).

IR (KBr pellet, 300 K): ν(C-D) = 2269 cm-1.

2-D-naphthalene (4):

H1 NMR (CDCl3, 300K): δ = 7.94-7.90 (m, 4H), 7.57-7.54 (m, 3H).

C13 NMR (CDCl3, 300K): δ = 125.7, 125.8, 127.7, 127.9, 133.4

GC-MS m/z (rel. int.): 129 (M+, 100).

IR (KBr pellet, 300 K): ν(C-D) = 2271 cm-1.

Supplementary figures

Fig. S1. Isotropic IR absorption spectra of naphthalene, 1-D-, and 2-D-naphthalene: (a) 10% solutions in CCl4, and (b) polycrystalline powders in KBr pellet.

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Fig. S2. Polarized IR spectra A(((() (blue) and A((() (red color) of naphthalene in nematic liquid crystal ZLI-1695 (after elimination of solvent absorption bands).

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Fig. S3. Polarized IR spectra A(((() (blue) and A((() (red color) of 1-D-naphthalene in nematic liquid crystal ZLI-1695 (after elimination of solvent absorption bands).

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Fig. S4. Polarized IR spectra A(((() (blue) and A((() (red color) of 2D-naphthalene in nematic liquid crystal ZLI-1695 (after elimination of solvent absorption bands).

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Fig. S5. Raman spectra of naphthalene, 1-D- and 2-D-naphthalene (top to bottom); polycrystalline powders in KBr-pellet.

Fig. S6. (a) Experimental and (b) theoretically predicted Raman spectrum of naphthalene.

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Fig. S7. (a) Experimental and (b) theoretically predicted IR spectrum of naphthalene.

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Fig. S8. (a) Experimental and (b) theoretically predicted Raman spectrum of 1D-naphthalene.

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Fig. S9. (a) Experimental and (b) theoretically predicted IR spectrum of 1-D-naphthalene.

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Fig. S10. (a) Experimental and (b) theoretically predicted Raman spectrum of 2-D-naphthalene.

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Fig. S11. (a) Experimental and (b) theoretically predicted IR spectrum of 2-D-naphthalene.

Table S1. Results from least squares optimization of the scale factors of naphthalene, 1-D-naphthalene and 2-D-naphthalene.

|No. |Description |Initial transferable |Optimized scale factorsb |

| | |scale factorsa | |

| | | |#1 |#2 |#3 |#4 |#5 |#6 |#7 |

|1 |C-H, C-D stretch |0.9182 |0.91349 |0.92422 |0.92443 |0.92047 |0.92402 |0.93112 |0.94713 |

|2 |C-C stretch |0.9254 |0.92890 |0.95491 |0.95494 |0.94330 |0.95872 |0.93583 |0.96591 |

|3 |C-H, C-D in-plane bending |0.9473 |0.94258 |0.96129 |0.96146 |0.98729 |0.95229 |0.95119 |0.96181 |

|4 |C-C-C ring bending |0.9923 |0.97913 |0.96658 |0.96648 |0.98336 |0.95969 |0.98743 |0.98358 |

|5 |C-H, C-D out-of-plane bending |0.9711 |0.96232 |0.95216 |0.95899 |0.94359 |0.93733 |0.95730 |0.92902 |

|6 |All torsionsc |0.9389 |0.93890 |0.93890 |0.93890 |0.93890 |0.93890 |0.93890 |0.93890 |

a Initial scale factors taken from Baker at al. [19] (recommended for use at B3LYP/6-31G* level).

b Notation: #1 - B3LYP/6-31G*; #2 - B3LYP/6-311+G**; #3 - B3LYP/6-311++G**; #4 - B3LYP/aug-cc-pVDZ; #5 - B3LYP/aug-cc-pVTZ; #6 - B3LYP/6-31G*/IEF PCM; #7- B3LYP/aug-cc-pVTZ/IEF PCM.

c Not refined.

Table S2

IR active normal modes of naphthalene calculated by the SQM FF method at B3LYP/6-311++G** level, and orientation parameters Kf of observed band polarization directions derived from IR-LD measurements.

|ModeNo. |Experimental |Calculated |

| |Sym. species |ν (cm-1) |

| | |IR & Raa |

| |Sym. species |ν (cm-1) |

| | |IR& Raa |

|Sym. species |ν (cm-1)

IR and Ramana |ν (cm-1)

IR-LD |Kf

||(p,f|

(deg.) |ν(cm-1) |(c,f

(deg.) |My,f |Mz,f |PED (%) | |1 |33A΄ |3069 |3069 sh |0.453 |30.6 |3066 |-2.1 |0.1534 |-4.2415 |νCH (99) | |2 | |3061 |3062 sh |0.391 |53.3 |3059 |45.9 |-3.5274 |-3.4168 |νCH (99) | |3 | |3057 |3055 s |0.361 |65.4 |3054 |-87.1 |5.3721 |-0.2751 |νCH (99) | |4 | |3048 |- |- |- |3045 |-74.0 |2.7720 |-0.7928 |νCH (99) | |5 | |3043 |3043 sh |0.361 |65.4 |3041 |-87.7 |1.9745 |-0.0761 |νCH (99) | |6 | |3035 |- |0.454 |30.2 |3039 |-59.6 |-1.7366 |1.0180 |νCH (99) | |7 | |3029 |3017 w |0.402 |49.3 |3036 |74.2 |-0.8991 |-0.2552 |νCH (99) | |8 | |2271 |2274 w |0.431 |38.9 |2259 |-36.7 |-1.5894 |2.1358 |νCD (96) | |9 | |1625 |1628 vw |0.338 |79.9 |1630 |-89.4 |0.3279 |-0.0032 |νCC (66), αCCC(17), βCH(17) | |10 | |1587 |1590 m |0.337 |81,0 |1595 |-87.9 |1.4576 |-0.0528 |νCC (68), βCH(24), αCCC( 6) | |11 | |1576 |1573 vw |0.438 |36.4 |1575 |-16.3 |0.0585 |-0.2005 |νCC (72), αCCC(14), βCH(13) | |12 | |1502 |1504 s |0.488 |12.0 |1508 |-3.8 |0.1783 |-2.7059 |νCC (56), βCH(39) | |13 | |1456 |1449 |- |- |1454 |-6.8 |0.0093 |-0.0784 |βCH(68), νCC (30) | |14 | |1437 |1437 w |- |- |1438 |-72.2 |-0.8775 |0.2809 |βCH(49), νCC (41), αCCC( 6) | |15 | |1381 |1390 vw |0.355 |68.4 |1368 |82.5 |0.2832 |0.0373 |νCC(93) | |16 | |1363 |1364 w |0.353 |69.5 |1363 |58.9 |-1.1186 |-0.6750 |νCC (54), βCH(42) | |17 | |1355 |1353 w |0.351 |70.5 |1355 |-62.3 |-1.0655 |0.5587 |νCC (52), βCH(36), βCD( 7) | |18 | |1269 |1268 m |0.337 |81.0 |1261 |-89.8 |-2.6152 |0.00762 |βCH(48), νCC (31), αCCC(21) | |19 | |1238 |1239 w |0.371 |61.0 |1241 |-47.2 |0.1042 |-0.0966 |βCH(58), αCCC(21), νCC (20) | |20 | |1196 |1195 w |0.494 |4.5 |1195 |-7.6 |0.1211 |-0.9116 |νCC(63), βCH(35) | |21 | |1157 |1155 vw |0.429 |39.7 |1155 |-37.7 |0.2935 |-0.3798 |βCH(72), νCC(26) | |22 | |1141 |1142 vw |0.493 |6.4 |1146 |-2.6 |0.0351 |-0.7693 |βCH(61), νCC(38) | |23 | |1130 |1131 w-m |0.336 |82.2 |1132 |83.9 |-2.0837 |-0.2219 |βCH(48), νCC(30), αCCC(22) | |24 | |1027 |1031 w |0.457 |29.0 |1028 |-33.3 |0.6235 |-0.9487 |νCC(66), βCH(24), βCD( 7) | |25 | |1011 |1014 m |0.490 |10.1 |1015 |-6.7 |0.3155 |-2.6872 |νCC(80), βCH(16) | |26 | |950 |938 vw |0.394 |52.2 |935 |49.2 |0.3376 |0.2917 |αCCC(86), νCC ( 7) | |27 | |881 |883 w-m |0.392 |52.9 |881 |45.3 |-0.9264 |-0.9153 |βCD(59), νCC(24), αCCC(16) | |28 | |784 |- |- |- |779 |-74.2 |0.1962 |-0.0557 |αCCC(63), νCC(27), βCD( 6) | |29 | |746 |- |- |- |747 |48.8 |0.0725 |0.0634 |νCC(64), αCCC(23), βCD( 9) | |30 | |614 |616 m |0.494 |4.5 |622 |0.7 |-0.0213 |-1.8663 |αCCC(90) | |31 | |511 |- |- |- |509 |-4.7 |-0.0022 |0.0266 |αCCC(75), νCC (22) | |32 | |505 |- |- |- |504 |-17.9 |0.0036 |-0.0111 |αCCC(76), νCC (21) | |33 | |355 |- |- |- |355 |88.9 |-1.2472 |-0.0231 |αCCC(73), νCC (22) | |34 |15A˝ |975 |967 sh |- |- |975 |oop |0.0000 |0.0000 |γCH(87), τΒCC(12) | |35 | |963 |961 w |0.209 |- |956 |oop |0.0000 |0.0000 |γCH(87), τΑCC(10) | |36 | |953 |949 w |- |- |940 |oop |0.0000 |0.0000 |γCH(89), τΒCC( 7) | |37 | |906 |905 m |0.177 |- |906 |oop |0.0000 |0.0000 |γCH(77), τΑCC(14), γCD( 5) | |38 | |868 |865 m-s |0.172 |- |866 |oop |0.0000 |0.0000 |γCH(77), τΒCC(12), τΑCC( 7) | |39 | |826 |824 s |0.172 |- |825 |oop |0.0000 |0.0000 |γCH(87), γCD( 6) | |40 | |777 |769 sh |0.181 |- |761 |oop |0.0000 |0.0000 |τΒCC(44), τΑCC(41), γCH(14) | |41 | |753 |755 vs |0.172 |- |756 |oop |0.0000 |0.0000 |γCH(77), γCD(11), τΑCC( 6) | |42 | |667 |664 m-s |0.184 |- |662 |oop |0.0000 |0.0000 |γCD(51), γCH(21), τΑCC(19), τΒCC( 9) | |43 | |595 |595 w-m |0.182 |- |590 |oop |0.0000 |0.0000 |τΒCC(44), τΑCC(28), γCH(24) | |44 | |483 |477 vs |0.171 |- |477 |oop |0.0000 |0.0000 |τΑCC(29), τΒCC(28), τΑΒ(28), γCH(11) | |45 | |452 |450 w |0.172 |- |450 |oop |0.0000 |0.0000 |τΑCC(44), τΒCC(38), γCH(18) | |46 | |387 |- |- |- |382 |oop |0.0000 |0.0000 |τΒCC(43), τΑCC(40), γCH(16) | |47 | |- |- |- |- |182 |oop |0.0000 |0.0000 |τΑCC(47), τΒCC(46) | |48 | |- |- |- |- |167 |oop |0.0000 |0.0000 |τΑΒ(29), τΑCC(25), τΒCC(23), γCH(23) | |

Comments:|(p,f| and (c,f are predicted and calculated angles between transition moments and long (z) molecular axis; My,f and Mz,f are y and z components of f th transition moment Mf in coordinate system used in DFT calculations; PED is potential energy distribution.

a Combined values from IR spectrum of 10 % CCl4 solution and/or from Raman spectrum of polycrystalline powder;

Derivatives of Kz with respect to K1, K2 and tan(γ)

[pic], (S1)

[pic], (S2)

[pic] (S3)

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