Organic & Biomolecular Chemistry
Page 6 of 8
interactionꢀofꢀflatꢀribbonsꢀ(Figureꢀ5dꢀandꢀS13).ꢀTheꢀcomplexationꢀ
potassiumꢀ carbonateꢀ wasꢀ addedꢀ (3.11ꢀ g,ꢀ 22.50ꢀ mmol).ꢀ Theꢀ
ofꢀ12GAꢀbyꢀreceptorꢀ1ꢀobservedꢀinꢀsolutionꢀcouldꢀgivesꢀriseꢀtoꢀ
supramolecularꢀplatformsꢀ withꢀ aꢀ largerꢀ πꢁsurfaceꢀ endowedꢀwithꢀ
manyꢀparaffinicꢀchains.ꢀTheꢀinterdigitationꢀofꢀtheꢀchainsꢀandꢀtheꢀ
5ꢀ πꢁπꢀstackingꢀbetweenꢀtheꢀaromaticꢀcagesꢀwouldꢀformꢀtheꢀlamellaeꢀ
constitutiveꢀofꢀtheꢀflatꢀribbons.ꢀ
reactionꢀmixtureꢀwasꢀstirredꢀforꢀthreeꢀhours.ꢀAfterꢀevaporationꢀofꢀ
theꢀsolventꢀunderꢀreducedꢀpressure,ꢀtheꢀresidueꢀwasꢀwashedꢀwithꢀ
water,ꢀextractedꢀwithꢀmethyleneꢀchloride,ꢀdriedꢀoverꢀMgSO4,ꢀandꢀ
1
furtherꢀ purificationꢀ (310ꢀ mg,ꢀ 73%).ꢀ Mp:ꢀ 114.5ꢁ115.6ꢀ ºC;ꢀ Hꢀ
NMRꢀ(CDCl3,ꢀ300ꢀMHz):ꢀδꢀppmꢀ7.83ꢀ(d,ꢀJꢀ=ꢀ1.4ꢀHz;ꢀ2H,ꢀHb),ꢀ
7.70ꢀ(t,ꢀJꢀ=ꢀ1.4ꢀHz,ꢀ1H,ꢀHa),ꢀ6.12ꢀ(br,ꢀ1H,ꢀHd),ꢀ3.45ꢀ(m,ꢀ2H,ꢀHe),ꢀ
3.14ꢀ (s,ꢀ 2H,ꢀ Hc),ꢀ 1.60ꢀ (m,ꢀ 2H,ꢀ Hf),ꢀ 1.34ꢁ1.27ꢀ (br,ꢀ 14H,ꢀ
65ꢀ Hg+h+i+j+k+l+m),ꢀ 0.89ꢀ (t,ꢀ Jꢀ =ꢀ6.8ꢀHz;ꢀ 3H,ꢀ Hn);ꢀ 13Cꢀ NMRꢀ (CDCl3,ꢀ
75Mz):ꢀδꢀppmꢀ165.7,ꢀ137.8,ꢀ135.6,ꢀ130.7,ꢀ123.1,ꢀ81.8,ꢀ78.9;ꢀFTIRꢀ
(neat):ꢀνꢀ653,ꢀ692,ꢀ759,ꢀ845,ꢀ891,ꢀ982,ꢀ1075,ꢀ1167,ꢀ1251,ꢀ1329,ꢀ
1425,ꢀ 1461,ꢀ 1545,ꢀ 1585,ꢀ 1640,ꢀ 1814,ꢀ 2159,ꢀ 2856,ꢀ 2926,ꢀ 3073,ꢀ
3310ꢀ cm–1.ꢀ HRMSꢀ (ESIꢁFT)ꢀ m/zꢀ calcd.ꢀ forꢀ C21H28NOꢀ [M+H]+,ꢀ
70ꢀ 310.217089;ꢀfound,ꢀ310.21654.ꢀ
Experimental
3,5-dibromo-N-decylbenzamide (3).ꢀ 3,5ꢁdibromobenzoicꢀ acidꢀ
(1.78ꢀ g,ꢀ 6.36ꢀ mmol),ꢀ 1ꢁethylꢁ3ꢁ(3ꢁdimethylaminopropyl)ꢁ
10ꢀ carbodiimideꢀ hydrochlorideꢀ (1.34ꢀ g,ꢀ 6.99ꢀ mmol)ꢀ andꢀ 4ꢁ
dimethylaminopyridineꢀ (0.85ꢀ g,ꢀ 6.99ꢀ mmol)ꢀ wereꢀ dissolvedꢀ inꢀ
dryꢀ dichloromethaneꢀ (80ꢀ mL)ꢀ underꢀ argonꢀ atmosphereꢀ atꢀ 0ꢀ ºC.ꢀ
Theꢀ mixtureꢀ wasꢀ stirredꢀ forꢀ 15ꢀ minutesꢀ andꢀ thenꢀ 1ꢁdecylamineꢀ
(1.3ꢀmL,ꢀ6.36ꢀmmol)ꢀwasꢀaddedꢀdropwise.ꢀTheꢀreactionꢀmixtureꢀ
15ꢀ wasꢀallowedꢀtoꢀwarmꢀupꢀtoꢀroomꢀtemperatureꢀandꢀwasꢀstirredꢀforꢀ
3ꢀhours.ꢀTheꢀorganicꢀlayerꢀwasꢀwashedꢀwithꢀHClꢀ1Mꢀandꢀwater,ꢀ
driedꢀwithꢀMgSO4,ꢀfiltered,ꢀandꢀtheꢀsolventꢀwasꢀremovedꢀunderꢀ
reducedꢀ pressure.ꢀ Theꢀ residueꢀ wasꢀ purifiedꢀ byꢀ columnꢀ
chromatographyꢀ(silicaꢀgel,ꢀhexane:ethylꢀacetateꢀ5:1)ꢀaffordingꢀ3ꢀ
20ꢀ asꢀ aꢀ whiteꢀ solidꢀ (1.63ꢀ g,ꢀ 61%).ꢀ Mp:ꢀ 82.4ꢁ84.3ꢀ ºC;ꢀ 1Hꢀ NMRꢀ
(CDCl3,ꢀ300ꢀMHz):ꢀδꢀppmꢀ7.74ꢀ(d,ꢀJꢀ=ꢀ1.7ꢀHz,ꢀ2H,ꢀHb),ꢀ7.71ꢀ(t,ꢀJꢀ
=ꢀ1.7ꢀHz;ꢀ1H,ꢀHa),ꢀ5.91ꢀ(br,ꢀ1H,ꢀHc),ꢀ3.36ꢀ(m,ꢀ2H,ꢀHd),ꢀ1.54ꢀ(m,ꢀ
2H,ꢀHe),ꢀ1.27ꢁ1.20ꢀ(br,ꢀ14H,ꢀHf+g+h+i+j+k+l),ꢀ0.81ꢀ(t,ꢀJꢀ=ꢀ6.5ꢀHz,ꢀ3H,ꢀ
Hm);ꢀ13CꢀNMRꢀ(CDCl3,ꢀ75Mz):ꢀδꢀppmꢀ165.2,ꢀ138.4,ꢀ136.9,ꢀ129.2,ꢀ
25ꢀ 123.5,ꢀ40.8,ꢀ32.2,ꢀ29.8,ꢀ29.6,ꢀ27.3,ꢀ23.0,ꢀ14.4;ꢀFTIRꢀ(neat):ꢀνꢀ674,ꢀ
717,ꢀ 739,ꢀ 767,ꢀ 866,ꢀ 899,ꢀ 1107,ꢀ 1158,ꢀ 1284,ꢀ 1310,ꢀ 1371,ꢀ 1411,ꢀ
1462,ꢀ1550,ꢀ1590,ꢀ1639,ꢀ2854,ꢀ2925,ꢀ3286ꢀcm–1.ꢀHRMSꢀ(ESIꢁFT)ꢀ
m/z:ꢀ calcd.ꢀ forꢀ C17H24Br2NOꢀ [MꢁH]+,ꢀ 416.022461;ꢀ found,ꢀ
416.02301.ꢀ
30ꢀ N-decyl-3,5-bis(2-(trimethylsilyl)ethynyl)benzamide (4).ꢀ 3,5ꢁ
dibromoꢁNꢁdecylꢁbenzamideꢀ (3)ꢀ (770ꢀ mg,ꢀ 1.93ꢀ mmol),ꢀ bisꢁ
(triphenylphosphine)ꢁpalladium(II)ꢁchlorideꢀ (133ꢀ mg,ꢀ 0.19ꢀ
mmol),ꢀcopperꢀ(I)ꢀiodideꢀ(19ꢀmg,ꢀ0.10ꢀmmol)ꢀandꢀtriethylamineꢀ
(1.1ꢀ mL,ꢀ 7.72ꢀ mmol)ꢀ wereꢀ dissolvedꢀ inꢀ dryꢀ THFꢀ (4ꢀ mL).ꢀ Theꢀ
35ꢀ mixtureꢀ wasꢀ subjectedꢀ toꢀ severalꢀ vacuum/argonꢀ cyclesꢀ andꢀ
trimethylsilylacetyleneꢀ (0.8ꢀ mL,ꢀ 5.80ꢀ mmol)ꢀ wasꢀ added.ꢀ Theꢀ
mixtureꢀ wasꢀ heatedꢀ atꢀ 70ꢀ ºCꢀ andꢀ stirredꢀ overnight.ꢀ Afterꢀ
evaporationꢀofꢀtheꢀsolventꢀunderꢀreducedꢀpressure,ꢀtheꢀcrudeꢀwasꢀ
washedꢀwithꢀHClꢀ1M,ꢀNH4Clꢀsaturatedꢀsolution,ꢀwater,ꢀextractedꢀ
40ꢀ withꢀmethylenechloride,ꢀandꢀfilteredꢀwithꢀcelite.ꢀTheꢀresidueꢀwasꢀ
purifiedꢀ byꢀ columnꢀ chromatographyꢀ (silicaꢀ gel,ꢀ hexane:ethylꢀ
acetateꢀ 20:1)ꢀ affordingꢀ 4ꢀ asꢀ aꢀbrownishꢀ oilꢀ (490ꢀ mg,ꢀ 56%).ꢀ 1Hꢀ
NMRꢀ(CDCl3,ꢀ300ꢀMHz):ꢀδꢀppmꢀ7.79ꢀ(d,ꢀJꢀ=ꢀ1.5ꢀHz,ꢀ2H,ꢀHb),ꢀ
6.69ꢀ(t,ꢀJꢀ=ꢀ1.5ꢀHz;ꢀ1H,ꢀHa),ꢀ6.17ꢀ(br,ꢀ1H,ꢀHd),ꢀ3.45ꢀ(m,ꢀ2H,ꢀHe),ꢀ
45ꢀ 1.61ꢀ(q,ꢀJꢀ=ꢀ6.8ꢀHz,ꢀ2H,ꢀHf),ꢀ1.36ꢁ1.30ꢀ(br,ꢀ14H,ꢀHg+h+i+j+k+l+m),ꢀ
0.91ꢀ(t,ꢀJꢀ=ꢀ6.5ꢀHz,ꢀ3H,ꢀHn),ꢀ0.27ꢀ(s,ꢀ18H,ꢀHc);ꢀ13CꢀNMRꢀ(CDCl3,ꢀ
75Mz):ꢀ δꢀ ppmꢀ 166.1,ꢀ 137.7,ꢀ 135.4,ꢀ 130.2,ꢀ 124.1,ꢀ 103.3,ꢀ 96.4,ꢀ
40.4,ꢀ32.1,ꢀ29.8,ꢀ29.7,ꢀ29.5,ꢀ27.2,ꢀ22.9;ꢀFTIRꢀ(neat):ꢀνꢀ640,ꢀ674,ꢀ
712,ꢀ 767,ꢀ 891,ꢀ 936,ꢀ 989,ꢀ 1067,ꢀ 1155,ꢀ 1247,ꢀ 1326,ꢀ 1373,ꢀ 1466,ꢀ
50ꢀ 1538,ꢀ 1586,ꢀ 1634,ꢀ 1817,ꢀ 2853,ꢀ 2921,ꢀ 2955,ꢀ 3067,ꢀ 3288ꢀ cm–1.ꢀ
HRMSꢀ (ESIꢁFT)ꢀ m/zꢀ calcd.ꢀ forꢀ C27H42NOSi2ꢀ [MꢁH]+,ꢀ
452.280495;ꢀfound,ꢀ452.28079.ꢀ
N-decyl-3,5-bis(1-biphenyl-1H-1,2,3-triazol-4-yl)benzamide (1).ꢀ
Compoundꢀ5ꢀ(126ꢀmg,ꢀ0.41ꢀmmol),ꢀ4ꢁbiphenylꢀazideꢀ(4)ꢀ(228ꢀmg,ꢀ
1.22ꢀ mmol),ꢀ copperꢀ sulphateꢀ pentahydrateꢀ (2ꢀ mg,ꢀ 0.008ꢀ mmol)ꢀ
andꢀsodiumꢀascorbateꢀ(4ꢀmg,ꢀ0.02ꢀmmol)ꢀwereꢀdissolvedꢀinꢀ4ꢀmLꢀ
75ꢀ ofꢀ aꢀ dichloromethane:waterꢀ mixtureꢀ (1:1)ꢀ andꢀ metallicꢀ copperꢀ
wasꢀaddedꢀtoꢀtheꢀmixtureꢀunderꢀArgonꢀatmosphere.ꢀTheꢀreactionꢀ
mixtureꢀwasꢀstirredꢀforꢀ72ꢀhoursꢀandꢀthen,ꢀtheꢀorganicꢀlayerꢀwasꢀ
separate,ꢀdriedꢀoverꢀMgSO4,ꢀandꢀfiltered.ꢀAfterꢀevaporationꢀofꢀtheꢀ
solventꢀ underꢀ reducedꢀ pressure,ꢀ theꢀ residueꢀ wasꢀ purifiedꢀ byꢀ
80ꢀ columnꢀchromatographyꢀ(silicaꢀgel,ꢀchloroform:methanolꢀ100:1)ꢀ
affordingꢀ 1ꢀasꢀaꢀlightꢀ yellowꢀsolidꢀ(223ꢀmg,ꢀ78%).ꢀMp:ꢀ 201.7ꢁ
202.7ꢀºC;ꢀ1HꢀNMRꢀ(CDCl3,ꢀ300ꢀMHz):ꢀδꢀppmꢀ8.58ꢀ(br,ꢀ1H,ꢀHa),ꢀ
8.38ꢀ(s,ꢀ2H,ꢀHc),ꢀ8.31ꢀ(d,ꢀJꢀ=1.3ꢀHz,ꢀ2H,ꢀHb),ꢀ7.85ꢀ(d,ꢀJꢀ=ꢀ8.6Hz,ꢀ
4H,ꢀHd),ꢀ7.75ꢀ(d,ꢀJꢀ=ꢀ8.6ꢀHzꢀ4H,ꢀHe),ꢀ7.63ꢀ(m,ꢀ4H,ꢀHf),ꢀ7.51ꢁ7.38ꢀ
85ꢀ (m,ꢀ6H,ꢀHg+h),ꢀ6.71ꢀ(t,ꢀJꢀ=ꢀ5.7ꢀHzꢀ1H,ꢀHi),ꢀ3.53ꢀ(m,ꢀ2H,ꢀHj),ꢀ1.70ꢀ
(q,ꢀJꢀ=ꢀ6.8ꢀHz,ꢀ2H,ꢀHk),ꢀ1.46ꢁ1.28ꢀ(br,ꢀ14H,ꢀHl+m+n+o+p+q+r),ꢀ0.89ꢀ
(t,ꢀJꢀ=ꢀ6.7ꢀHz,ꢀ3H,ꢀHs);ꢀ13CꢀNMRꢀ(CDCl3,ꢀ75Mz):ꢀδꢀppmꢀ166.7,ꢀ
147.2,ꢀ 141.9,ꢀ 139.5,ꢀ 136.2,ꢀ 135.9,ꢀ 131.3,ꢀ 129.0,ꢀ 128.4,ꢀ 128.0,ꢀ
127.1,ꢀ 125.3,ꢀ 123.9,ꢀ 120.7,ꢀ 118.3,ꢀ 40.4,ꢀ 31.9,ꢀ 29.7,ꢀ 29.6,ꢀ 29.4,ꢀ
90ꢀ 29.3,ꢀ27.1,ꢀ22.7,ꢀ14.1;ꢀFTIRꢀ(neat):ꢀ νꢀ626,ꢀ647,ꢀ658,ꢀ695,ꢀ 722,ꢀ
763,ꢀ841,ꢀ892,ꢀ991,ꢀ1042,ꢀ1117,ꢀ1234,ꢀ1296,ꢀ1402,ꢀ1459,ꢀ1491,ꢀ
1527,ꢀ 1610,ꢀ 1643,ꢀ 2363,ꢀ 2854,ꢀ 2924,ꢀ 3062,ꢀ 3138,ꢀ 3291ꢀ cm–1;ꢀ
HRMSꢀ(ESIꢁFT)ꢀm/zꢀcalcd.ꢀforꢀ[C45H46N7O]+:ꢀ700.37584;ꢀfound,ꢀ
700.37608.ꢀ
95ꢀ Computational details.
Allꢀ theoreticalꢀ calculationsꢀ wereꢀ carriedꢀ outꢀ withinꢀ theꢀ densityꢀ
functionalꢀtheoryꢀ(DFT)ꢀapproachꢀbyꢀusingꢀtheꢀC.01ꢀrevisionꢀofꢀ
theꢀ Gaussianꢀ 09ꢀ programꢀ package.20ꢀ DFTꢀ calculationsꢀ wereꢀ
performedꢀ usingꢀ theꢀ hybridꢀ metaꢀ exchangeꢁcorrelationꢀ M06ꢁ2Xꢀ
100ꢀ functional,ꢀ whichꢀ hasꢀ beenꢀ speciallyꢀ designedꢀ toꢀ accountꢀ forꢀ
noncovalentꢀinteractions.21ꢀGeometryꢀoptimizationsꢀwereꢀcarriedꢀ
outꢀwithꢀtheꢀM06ꢁ2Xꢀfunctionalꢀinꢀcombinationꢀwithꢀtheꢀstandardꢀ
6ꢁ311G**ꢀbasisꢀset.22ꢀTheꢀalkylꢀchainsꢀattachedꢀtoꢀtheꢀnitrogenꢀofꢀ
theꢀamideꢀgroupꢀinꢀreceptorꢀ1ꢀandꢀformingꢀtheꢀalkoxyꢀgroupsꢀofꢀ
105ꢀ 12GAꢀ wereꢀ substitutedꢀ byꢀ methylꢀ groupsꢀ toꢀ reduceꢀ theꢀ
computationalꢀ cost.ꢀ Onꢀ theꢀ previouslyꢀ optimizedꢀ structures,ꢀ
singleꢁenergyꢀ calculationsꢀ atꢀ theꢀ M06ꢁ2X/6ꢁ311G**ꢀ levelꢀ wereꢀ
performedꢀ toꢀ computeꢀ theꢀ bindingꢀ energies.ꢀ Theꢀ basisꢀ setꢀ
superpositionꢀ errorꢀ (BSSE)ꢀ affectingꢀ theꢀ bindingꢀ energiesꢀ wasꢀ
110ꢀ correctedꢀ byꢀ usingꢀ theꢀ standardꢀ counterpoiseꢀ method.23ꢀ Theꢀ
BSSEꢀisꢀestimatedꢀtoꢀbeꢀalmostꢀnegliglibleꢀforꢀ1•X−ꢀcomplexesꢀ
N-decyl-3,5-diethynylbenzamide
(trimethylsilyl)ethynyl)ꢁbenzamideꢀ(4)ꢀ(639ꢀmg,ꢀ1.39ꢀmmol)ꢀwasꢀ
55ꢀ dissolvedꢀ inꢀ 20ꢀ mLꢀ ofꢀ aꢀ THF:methanolꢀ mixtureꢀ (1:1)ꢀ andꢀ
(5).ꢀ
Nꢁdecylꢁ3,5ꢁbis(2ꢁ
6
| Journal Name, [year], [vol], 00–00
This journal is © The Royal Society of Chemistry [year]