The PCN-222 series he h ptterns of the gxEPPP series nd"for rystlline smples"the (t from ietveld re(nements 40 re shown in pigF PF he identity of the ten smples vries widelyX the h pttern of gxEPPP is hrterised y the intense IHH re)etion @2θ ∼ 2 °for gu K α1 rditionAD nd while this is present in most smples @ePD fPD gPD pPD qPD sPD nd tPAD its reltive intensity vries drstillyF his indites phse mixturesD whih is lso supported y iw pigF I!PF gxEPPP ppers s long rods with ler hexgonl symmetryD yet severl morphologies"often ues or similr"re typilly oservle s wellF hree smples @hPD iPD rPA did not yield ny gxEPPP produtX rP is lrgely morphousD iP orresponds to phseEpure dgxEPPR nd hP will e disussed elowF he results showse surprisingly wide vriety of outomes from n identil syntheti reipeF ietveld re(nements llow the phses present to e extrted nd qunti(ed rs in pigF PF gution is however requiredX he reltively poor qulity of the lortory h V pigure PX he h ptterns of the IH smples from the gxEPPP seriesD with rude nd tivted wyps to the left nd rightD respetivelyF he experimentl dt re shown in lk with the lulted ietveld (ts in red nd the inserted r hrts show the phse frtions otined from the re(nementF golour odeX grey denotes P m 3m @dgxEPPRAD purple I4 1 /amd @gxEPPSAD nd green P 6/mmm @gxEPPPAF hshed grey rs denote uiElike intermedite nd rossed white rs indite smples tht nnot e (tted y the forementioned phsesF he low smple quntity of sP prevented tivtionF λ = 1.5418 ÅF dt nd the multiple phses often render the (ts hllengingD prtiulrly for less rystlline smplesF he reltive intensities of re)etions n e hevily in)uened y solvent nd pore ontentD whih lso inreses the unertintyF purthermoreD the phse frtions do not ount for ny morphous ontent nd therefore only represent the rystlline prt of the smpleF he morphous ontent ws qunti(ed for few smplesD nd s n exmpleD the morphous phse frtion of tivted eP is ∼ 21% pigF UF roweverD this is rough estimteD s quntifying morphous ontents is hllengingF hespite these vetsD pigF P W provides useful pproximtion of the rystlline phse frtions of the ten smplesF helving deeper into pigF PD six smples re omintions of known r!porphyrin wypsF iP nd sP onsist of pure dgxEPPR nd gxEPPPD respetivelyY fPD gPD nd qP re mixtures of these wypsY nd pP n e (tted y omintion of gxEPPP nd gxEPPS pigF PF he remining four ompounds o'er some surprisesX eP nd tP ontin re)etions hrE teristi of gxEPPP nd gxEPPSD ut lso strong pek t ∼ 4.5°F his ould normlly e ttriuted to the ui gxEPPRD ut the remining re)etions expeted from this phse re sentF uh di'rtion pttern"denoted y hshed grey r in pigF P"resemles tht ttriuted to n intermedite phse @phse ss4A in the formtion of dgxEPPRD onsisting of r 6 @yrA 4 y 4 lusters with prtil orderF 27 hP nd rP re disussed elowF etivtion using rgl gretly 'ets the smplesD in prtiulr those feturing the preE sumed tetrgonl gxEPPSF his tetrgonl phse vnishes ompletely from the three smE ples where it ws present @ePD pPD tPA upon tivtionF he hnges re prtiulrly noE tle in pPD whih orresponds to phseEpure gxEPPP following tivtionF he instility towrds tivtion implies tht re)etions ssigned s gxEPPS do not orrespond to rysE tlline wypD ut rther n intermedite produtF vike most r!porphyrin systemsD gxEPPS is highly stle nd should survive the hrshly idi environment found during tivtionF 41 he presumed intermedite might dissolve or form rystlline gxEPPP or gxEPPR during the tivtion stepF elterntivelyD it nnot e exluded tht the gxEPPS prtiles"if smller thn the remining phses"were lost during the wshing following tivtionF etivtion typilly improves qulity of the ietveld re(nements for the rystlline smE plesD s removing unreted strting mterilGsolvent etc. from the pores enhnes the simiE lrity with the solventEfree rystl strutures from litertureF sn dditionD the phse frtions often hnge slightly fter tivtionF hile this my result from the loss of smll prtiles during wshingD the improvement of the (t due to solvent removl likely domintes nd the phse frtions for the tivted smples re thus more urteF he verge phse frtion of gxEPPP n e de(ned s 1 imilrly to the gxEPPP seriesD the gxEPPR series ontins vriety of produts pigF QF hree smples @eRD fRD sRA onsist of lrgely phseEpure dgxEPPR @P m 3mAD yet not single smple orresponds to the trgeted linkerEordered gxEPPR @Im 3mAF eR ontins hrdly visile re)etion t ∼ 5 °D presumly from minor impurity phseF hile eR nd fR feE ture ui nd uothedrl morphologyD the prtiles of sR show no ler fets pigF RF gRD qRD nd tR re mixtures of dgxEPPR nd gxEPPP"the ltter esily identi(ed y the IHH re)etion t P°nd the rodElike morphology pigF QDRF he remining four smples onsist of lowErystlline produtsD inluding the intermedite phse ss4 @iRD pRD rRA disE ussed oveF 27 iR lso fetures re)etions reminisient of tetrgonl gxEPPSF yverllD the produts otined from the gxEPPR synthesis re highly heterogeneous pigF QD lthough the spred is perhps slightly lower thn for the gxEPPP seriesF II pigure QX he h ptterns of the IH smples from the gxEPPR seriesD with rude nd tivted wyps to the left nd rightD respetivelyF he dt re shown in lk with ietveld (ts in red nd the inserted r hrts show the phse frtions otined from the re(nementF golour odeX grey denotes P m 3m @dgxEPPRAD purple I4 1 /amd @gxEPPSAD green P 6/mmm @gxEPPPAD light green P 6/m @gxEPPQAF hshed grey rs denote uiElike intermedite nd rossed white rs indite smples tht nnot e (tted y the forementioned phsesF λ = 1.5418 ÅF gxEPPR 13 nd dgxEPPR 17 "originlly known s gxEPPI 14 "shre the sme ui symmetry ut di'er in the extent of sptil linker orderF he superstruture of gxEPPR yields Im 3m symmetryD wheres the verge struture of the disordered dgxEPPR dopts the spe group P m 3mF urprisinglyD no smple in the gxEPPR series shows longErnge linker orderD lthough lolly ordered domins with short orreltion lengths nnot e exE ludedF he linker order originlly oserved in gxEPPR hene ppers elusive nd hllengE ing to ess synthetillyF vol linkerGvny order n hve funtionl implitionsD IP nd hene further studies into the linker rrngement in dgxEPPRGgxEPPR would e vluE leF etivtion normlly enhnes the qulity of the ietveld (ts for the rystlline smplesD wheres poorly ordered smples often morphiseF por exmpleD the ietveld (t of fR is notiely improved following tivtionD wheres hR loses its frgg re)etionsF roweverD few interesting ounterexmples to this generl trend existF pirstD rude pR only fetures hndful of di'rtion peksD yet n e well (tted y omintion of dgxEPPR nd gxE PPQ @P 6/mA when tivtedF he onverse senrio ours for tRD whih onsists of gxEPPP nd gxEPPR prior to tivtionD ut is lrgely morphous fterwrdD lthough the rodElike morphology hrteristi of gxEPPP is retined pigF RF es mentionedD the gxEPPS phse in iR vnishes fter tivtionD suggesting tht it might orrespond to n intermediteF he verge phse frtion of ui r!porphyrin wyps is ∼RV7 efore tivtion nd SQ7 fterY howeverD the disordered dgxEPPR @P m 3mA is exlusively otined over the ordered gxEPPR @Im 3mAF reneD if dgxEPPR nd gxEPPR re onsidered distint phsesD the suess rte is H7F eprt from the dditionl omplitions regrding the linker @disAorderD the results gree with the oservtions mde for gxEPPPF e vet regrding gxEPPQ"s seen in tivted pR"is in orderF gxEPPQ rystllises in P 6/m with disordered IPEfold oordinted r 6 @yrA re lerly insu0ient to imprt full ontrol over phse seletivityF es seen in the sD slight di'erenes pper in e.g. the size of the retion vil @PH!SH mlAD regent purityD soking time etween wshes @minutes!hoursAD drying time @overnight to over weekendAD nd dissolution method @sonition or notAF esertining the in)uene of eh of these hnges requires